Reactive dyes containing substituted 4-fluoropyridaz-6-one radicals

ABSTRACT

Compounds of the general formula I ##STR1## wherein R 1  is hydrogen, fluorine, chlorine or bromine, R 2  is hydrogen, fluorine, chlorine, bromine, or nitro, B is aliphatic or a sulfo-substituted phenylene radical, and X is a dye radical, are useful for dyeing hydroxyl-containing textile material, in particular cotton.

This application is a continuation of application Ser. No. 579,355,filed on Feb. 13, 1984 abandoned.

The present invention relates to compounds of the general formula I##STR2## where R¹ and R² independently of one another are each aradical, B is a direct bond or a bridge member and X is a dye radical.

R¹ and R² independently of one another can each be hydrogen, halogen,nitro, cyano, acylamino, hydroxyl, alkoxy, aryloxy, mercapto, alkylthio,arylthio, hydroxycarbonyl, alkoxycarbonyl, aryloxycarbonyl,aminocarbonyl, hydroxysulfonyl, alkylsulfonyl, arylsulfonyl,aminosulfonyl or an unsubstituted or substituted aliphatic, araliphatic,aromatic or heterocyclic radical.

R¹ and R² can each be, in particular, hydrogen, fluorine, chlorine,bromine, nitro, C₁ -C₄ -alkyl, alkoxy, alkoxycarbonyl or alkylsulfonyl,or unsubstituted or substituted phenyl.

Specific examples of radicals R¹ and R², in addition to those mentionedabove, are acetylamino, propionylamino, methyl, ethyl, n- and i-propyl,n-, i-, s- and t-butyl, cyclopentyl, cyclohexyl, phenyl, 2-naphthyl,benzyl, methoxy, ethoxy, n- and i-propyloxy, n-, i- s- and t-butoxy,phenoxy, 1- and 2-naphthyloxy, benzyloxy, methylthio, ethylthio, n- andi-propylthio, phenylthio, methoxycarbonyl, ethoxycarbonyl, n- andi-propoxycarbonyl, n-, i- s-, and t-butoxycarbonyl, phenoxycarbonyl,benzyloxycarbonyl, 1- and 2-naphthyloxycarbonyl, methylsulfonyl,ethylsulfonyl, phenylsulfonyl, 2-, 3- and 4-methylphenyl, 2-, 3- and4-nitrophenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and4-hydroxycarbonylphenyl, 2-, 3- and 4-hydroxysulfonylphenyl, 1-pyrrolyl,1-methyl-2- and -3-pyrrolyl, 2- and 3-thiophenyl, 2- and 3-furanyl, 2-and 3-tetrahydrofuranyl, 2-, 3- and 4-pyridyl, 1,4-dioxan-2- and -3-yl,1-imidazolyl, 1-methyl-2-, -4- and -5-imidazolyl, 1-pyrazolyl,1-methyl-2- and -3-pyrazolyl, 2-, 4- and 5-thiazolyl, 3-, 4- and5-isothiazolyl, 2-, 4- and 5-oxazolyl, 3-, 4- and 5-isoxazolyl, 3- and4-pyridazinyl, 2-, 4- and 5-pyrimidinyl, 2- and 3-pyrazinyl, 1-indolyl,1-propyl-2-, -3-, -4-, -5-, -6- and -7-indolyl, 2-, 3-, 4-, 5-, 6- and7-benzothiophenyl, 2-, 3-, 4-, 5-, 6- and 7-benzofuranyl, 2-, 3-, 4-,5-, 6-, 7- and 8-quinolyl, 1-, 3-, 4-, 5-, 6-, 7- and 8-isoquinolyl, 1-benzimidazolyl, 1-methyl-2-, -4-, -5-, -6- and -7-benzimidazolyl,1-benzopyrazolyl, 1-ethyl-3-, -4-, -5-, -6- and -7-benzopyrazolyl, 2-,4-, 5-, 6- and 7-benzothiazolyl, 3-, 4-, 5-, 6- and 7-benzisothiazolyl,2-, 4-, 5-, 6- and 7-benzoxazolyl, 3-, 4-, 5-, 6- and 7-benzisoxazolyl,3-, 4-, 5-, 6-, 7- and 8-cinnolinyl, 1-, 4-, 5-, 6-, 7- and8-phthalazinyl, 2-, 4-, 5-, 6-, 7- and 8-quinazolinyl and 2-, 3-, 5-,6-, 7- and 8-quinoxalinyl.

Preferred radicals R¹ and R² are hydrogen, fluorine, chlorine, bromine,amino, acetylamino, hydroxyl, methoxy and phenyl, H, Cl and Br beingparticularly preferred.

Bridge members B can be aliphatic, aromatic, araliphatic or heterocyclicradicals, the two first-mentioned being preferred. The bridge members Beach carry groups which are suitable for bonding to the dye radical X,and can furthermore be substituted by substituents stated for R¹ and R².

Aliphatic bridge members are, in particular, alkylene radicals of notmore than 10 carbon atoms which can futhermore be interrupted by oxygen,sulfur or C₁ -C₄ -alkylimino and substituted by fluorine, chlorine,bromine, nitro, C₁ -C₄ -alkyl, aryl, cyano, hydroxycarbonyl or C₁ -C₄-alkoxycarbonyl, and, for bonding to X, carry an imino, carbonyl orsulfonyl group.

Specific examples of aliphatic bridge members are methyleneimine,methylmethyleneimine, ethyleneimine, 1- and 2-methylethyleneimine, 1-and 2-phenylethyleneimine, 1- and 2-cyanoethyleneimine, 1- and2-hydroxycarbonylethyleneimine, 1- and 2-methoxycarbonylethyleneimine,propyleneimine, butyleneimine, 1- and 2-fluoroethyleneimine, 1- and2-chloroethyleneimine, 1- and 2-nitroethyleneimine, methylenecarbonyl,ethylenecarbonyl, 1- and 2-methylethylenecarbonyl,2,2-dimethylethylenecarbonyl, 1- and 2-fluoroethylenecarbonyl, 1- and2-nitroethylenecarbonyl, ethylenesulfonyl, 1- and2-methylethylenesulfonyl and 1- and 2-fluoroethylenesulfonyl.

Preferred aliphatic bridge members are ethyleneimine andethylenecarbonyl bridges, which can be substituted by methyl, phenyl,hydroxycarbonyl or methoxycarbonyl, as well as the correspondingpropyleneimine radicals.

Aromatic bridge members B are, in particular, phenylene and naphthyleneradicals which in turn carry an imino, carbonyl or sulfonyl group andcan be substituted by, for example, fluorine, chlorine, bromine, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, nitro, hydroxyl,hydroxycarbonyl, hydroxysulfonyl or polyfluoroalkyl.

Specific examples of aromatic bridge members B are: ##STR3##

Preferred aromatic bridge members B are phenylene and naphthyleneradicals which carry imino, carbonyl or sulfonyl groups and can besubstituted by chlorine, amino, hydroxyl or hydroxysulfonyl.

Examples of araliphatic bridge members B are: ##STR4##

Preferred araliphatic bridge members are benzylene radicals which carryan imino, carbonyl or sulfonyl group and can be substituted by chlorine,amino, hydroxyl or hydroxysulfonyl.

Examples of heterocyclic bridge members B are: ##STR5##

Preferred heterocyclic bridge members B are derived from thiazole,benzothiazole, imidazole or 1,3,4-thiadiazole radicals which carry animino, carbonyl or sulfonyl group.

Azo dye radicals X are derived from, for example, the mono- or polyazoseries, and can also contain fiber-reactive radicals; they correspond tothe general formula II

    [D--N═N--K--

where D is a radical of an aromatic or heterocyclic diazo componentwhich may or may not contain azo groups, and K is a radical of acoupling component which may or may not contain azo groups.

The other fiber-reactive radicals can be bonded to D and/or K;preferably, one further fiber-reactive radical is present, but it isalso possible for 2 or 3 such radicals to be present. The furtherradicals can be identical or different, and also include the radical ofthe formula ##STR6##

In particular, X corresponds to the general formula ##STR7## where K hasthe above meanings, D is a radical of the aniline or aminonaphthaleneseries, m is an integer from 0 to 3, p is an integer from 0 to 2, A is afiber-reactive radical which is bonded directly or via a bridge member,and R³ is a substituent, the individual radicals R³ being identical ordifferent.

Examples of bridge members via which the radical A can be bonded are--NH--, --N(CH₃)--, --CH₂ --NH--, --N(CH₃)--CH₂ --, --C_(n) H_(2n)--NH--CO--, --C_(n) H_(2n) --CO--NH--, --C_(n) H_(2n) --SO₂ --NH--,--C_(n) H_(2n) --NH--SO₂ --, --Ar--CO--NH--, --Ar--NH--CO--, --Ar--SO₂--NH--, --Ar--NH--SO₂ -- and --Ar--N═N--, where n is an integer from 0to 4 and Ar is aryl.

Examples of preferred aliphatic radicals are --C₂ H₄ -- and --C₃ H₆ --.

Examples of Ar are ##STR8##

The fiber-reactive radical A may also correspond to the formula

    --A'--Z

where A' is a chloro- or fluorotriazinyl or pyrimidinyl radical bondedvia an imino, methylimino, iminomethylene or methyliminomethylenebridge, and Z is a reactive radical from the vinyl sulfone, allylsulfone, halopyridazinone or β-chloroethylamino sulfone series.

R³ is a substituent from the group comprising, for example, C₁ -C₄-alkyl, trifluoromethyl, acetyl, C₁ -C₄ -alkoxy, fluorine, chlorine,bromine, hydroxysulfonyl, C₁ -C₄ -alkylsulfonyl, hydroxycarbonyl, C₁ -C₄-alkoxycarbonyl, amino, C₁ -C₄ -alkylamino, nitro, cyano, acetylamino,benzoylamino, phenylamino, hydroxyl, aminocarbonyl, C₁ -C₄-monoalkylaminocarbonyl, C₁ -C₄ -dialkylaminocarbonyl, aminosulfonyl, C₁-C₄ -monoalkylaminosulfonyl, C₁ -C₄ -dialkylaminosulfonyl,N-phenylaminocarbonyl, N-phenylaminosulfonyl, phenyl, styryl,phenylsulfonyl, phenylazo and naphthylazo, and benzene rings in theabove-mentioned substituents can be further substituted byhydroxysulfonyl, hydroxycarbonyl, methyl, methoxy, chlorine, nitro,amino, acetylamino or hydroxyl.

Preferred radicals R³ are methyl, methoxy, chlorine, hydroxysulfonyl,hydroxycarbonyl, nitro, amino, acetylamino and hydroxyl.

Specific examples of fiber-reactive radicals A are derived from thefollowing compounds (in the text which follows, pyridazinonyl ispyridazin-6-on-1-yl): Acryloyl chloride, β-chloro- or β-bromopropionylchloride, chloroacetyl chloride, α,β-dichloro- or α,β-dibromopropionylchloride, 2,3-dichloroquinoxaline-5-carbonyl chloride,2,3-dichloroquinoxaline-6-carbonyl chloride, 2,3-dichloroquinazoline-5-or -6-sulfonyl chloride, 2,4-dichloroquinazoline-6- or -7-sulfonylchloride, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl chloride, 2,4,7-or 2,4,8-trichloroquinazoline-6-sulfonyl chloride,2,4-dichloroquinazoline-6-carbonyl chloride, 3- or4-allylsulfonylaniline, 3- or 4-vinylsulfonylaniline, 3- or4-(chlorovinylsulfonyl)-aniline, 4-(2'-chloroethylsulfonyl)-aniline,4-(β-hydroxyethylsulfonyl)-aniline, 3- or4-(β-sulfatoethylsulfonyl)-aniline, 3- or4-(β-sulfatoethylsulfonamido)-aniline, 2,6-dichloropyrimidine-4- or-5-carbonyl chloride, N-(β-sulfatoethylsulfonyl)-piperazine,2,6-dichloropyrimidine-5-sulfonyl chloride, 2,4,6-trichloropyrimidine,2,4,6-trichloro-5-methylpyrimidine, 2,4,6-tribromo-5-cyanopyrimidine,2,4,5,6-tetrachloropyrimidine, 2,4,6-trifluoropyrimidine,2,4,6-trifluoro-5-chloropyrimidine, 4,6-difluoro-5-chloropyrimidine,2-methylsulfonyl-4-chloro-6-methylpyrimidine,2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine,2-methylsulfonyl-4-chloropyrimidine-5-carbonyl chloride,2,4,6-trichloro-5-methylsulfonylpyrimidine,2,4,6-trifluoro-5-methylsulfonylpyrimidine,2-methyl-4,6-dichloro-5-methylsulfonylpyrimidine,2,4,5-trichloro-6-methylsulfonylpyrimidine,2,4,6-trichloropyrimidine-5-carbonyl chloride, tetrachloropyridazine,tetrafluoropyridazine, 3,6-dichloropyridazine-4-carbonyl chloride,1-(4'-aminophenyl)-4,5-dichloropyridazin-6-one,p-(4,5-dichloropyridazinonyl)-benzoyl chloride,β-(4,5-dichloropyridazinonyl)-propionyl chloride,p-(4,5-dichloropyridazinonyl)-benzenesulfonyl chloride,β-(4,5-dichloropyridazinonyl)-propylamine, 1-(3'- or4'-aminophenyl)-4-fluoro-5-chloropyridazin-6-one,p-(4-fluoro-5-chloropyridazinonyl)-benzoyl chloride,p-(4-fluoro-5-chloropyridazinonyl)-benzenesulfonyl chloride,β-(4-fluoro-5-chloropyridazinonyl)-propionyl chloride,β-(4-fluoro-5-chloropyridazinonyl)-propylamine, 3- or4-chloroethylaminosulfonylaniline, 2,2,3,3-tetrafluorocyclobutylcarbonylchloride, 2,3,3-trifluorocyclobutenylcarbonyl chloride,2,2,3,3-tetrafluorocyclobutylacryloyl chloride or1,4-dichlorophthalazine-6-carbonyl chloride.

Particular examples are cyanuric fluoride, cyanuric chloride, cyanuricbromide, 2,4-dichloro-6-methyltriazine, 2,4-dichloro-6-phenyltriazineand the primary condensates of cyanuric fluoride, chloride and bromidewith ammonia, amines, organic hydroxy and mercapto compounds, eg.methanol, ethanol, isopropanol, phenol, α-naphthol, β-naphthol,chlorophenols, cresols, sulfonated phenols, thiophenol, thioglycolicacid, methylmercaptan, dimethyldithiocarbamic acid,2-mercaptobenzothiazole, thioacetamide, methylamine, ethylamine,n-propylamine, dimethylamine, diethylamine, β-hydroxyethylamine,di-(-hydroxyethyl)-amine, piperidine, morpholine, β-methoxyethylamine,β-(4-sulfophenyl)-ethylamine, aminoacetic acid, N-methylaminoaceticacid, taurine, N-methyltaurine, aniline, N-methylaniline, toluidine,anisidine, aniline-2,5-, -2,4- and -3,5-disulfonic acid, o-, m- andp-anilinesulfonic acid, o-, m- and p-N-methylanilinesulfonic acid, o-,m- and p-aminobenzoic acid, 4- and 5-sulfo-2-aminobenzoic acid,2-aminotoluene-4-sulfonic acid, 5-amino-2-hydroxybenzoic acid,β-aminoethanesulfonic acid, N-methylaminoethanesulfonic acid and mono-and disulfonic acids of 1-amino- and 2-aminonaphthalene.

Reactive radicals Z are preferably bonded to the radical A' via nitrogenin the form of --NH-- or --NH--NH--, specific examples of Z beingderived from the following compounds:4-(β-sulfatoethylsulfonyl)-phenylhydrazine, 4-allylsulfonylaniline,3-allylsulfonylaniline, 4-(propen-1'-ylsulfonyl)-aniline,4-vinylsulfonylaniline, 3-(β-sulfatoethylsulfonyl)-aniline,4-(-sulfatoethylsulfonyl)-aniline, 4-(β-chloroethylsulfonyl)-aniline,1-(3'- or 4'-aminophenyl)-4,5-dichloropyridazin-6-one, 1-(3'- or4'-aminophenyl)-4-fluoro-5-chloropyridazin-6-one,β-(4,5-dichloropyridazinonyl)-propylamine,β-(4-fluoro-5-chloropyridazinonyl)-propylamine,3-(-chloroethylaminosulfonyl)-aniline, or4-(β-chloroethylaminosulfonyl)-aniline.

A' is preferably a triazinyl radical.

Aromatic radicals D of the diazo components of the aniline andaminonaphthalene series, which do not carry any fiber-reactive groups,are derived from, for example, amines of the formulae IVa-f: ##STR9##where m and p have the above meanings, R⁴ is hydrogen, methyl, ethyl,methoxy, ethoxy, acetyl, cyano, hydroxycarbonyl, hydroxysulfonyl, C₁ -C₄-alkoxycarbonyl, hydroxyl, aminocarbonyl, C₁ -C₄ -alkylaminocarbonyl,fluorine, chlorine, bromine or trifluoromethyl, R⁵ is hydrogen, methyl,ethyl, methoxy, ethoxy, cyano, hydroxycarbonyl, hydroxysulfonyl,acetylamino, C₁ -C₄ -alkoxycarbonyl, aminocarbonyl, C₁ -C₄-alkylaminocarbonyl, fluorine, chlorine, nitro, aminosulfonyl, C₁ -C₄-alkylaminosulfonyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl or phenoxy, Xis 0 or 1 and Y is a direct bond or one of the groups --NHCO--,--CONH--, --CO--, --NHSO₂ --, --SO₂ NH--, --SO₂ --, --CH═CH--, --CH₂--CH₂ --, --CH₂ -- --NH--, --O--, --S-- and --N═N--.

R⁴ is preferably H, CH₃, CH₃ O, Cl, COOH, SO₃ H or OH, R⁵ is preferablyH, CH₃, CH₃ O, Cl, COOH, SO₃ H or NHCOCH₃ --, and Y is preferably --SO₂--, --CO--, --CH═CH--, --N═N--, --CH₂ --CH₂ or --CH₂ --.

Specific examples of aromatic amines which do not possess afiber-reactive group, can be used as diazo components for thepreparation of the novel dyes and correspond to, for example, thegeneral formula (IVa), (IVb), (IVc) or (IVd) are aniline,2-methoxyaniline, 2-ethoxyaniline, 2-methylaniline,4-nitro-2-aminoanisole, 4-chloro-2-aminoanisole, 4-methylaniline,4-methoxyaniline, 2-nitro-4-aminoanisole, 2-methoxy-5-methylaniline,4-nitroaniline, 2-chloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline,2-nitro-4-methylaniline, 2,5-dimethoxyaniline, 2,5-dimethylaniline,2,4-dimethylaniline, 4-butylaniline, 2-nitro-4-nitroaniline,2,5-diethoxyaniline, 4-cyanoaniline, 2-chloroaniline, 3-chloroaniline,4-chloroaniline, 2,5-dichloroaniline, 4-chloro-2-nitroaniline,4-chloro-2-methylaniline, 3-chloro-2-methylaniline,4-chloro-2-aminotoluene, 4-(p-tolylsulfonyl)-aniline,2-ethoxy-1-napthylamine, 1-naphthylamine, 2-naphthylamine,4-benzoylamino-2-ethoxyaniline, 3-amino-4-methylbenzonitrile,4-methylsulfonylaniline, 2-trifluoromethylaniline,1-trifluoromethyl-3-chloroaniline, 2,4-dichloroaniline-5-carboxylicacid, 2-aminobenzoic acid, 4-aminobenzoic acid, 3-aminobenzoic acid,3-chloroaniline-6-carboxylic acid, aniline-2- or -3- or -4-sulfonicacid, 2,5-disulfoaniline, 2,4-disulfoaniline, 3,5-disulfoaniline,2-aminotoluene-4-sulfonic acid, 2-aminoanisole-4-sulfonic acid,2-aminoanisole-5-sulfonic acid, 2-ethoxyaniline-5-sulfonic acid,2-ethoxyaniline-4-sulfonic acid, 4-sulfo-2-aminobenzoic acid,2,5-dimethoxyaniline-4-sulfonic acid, 2,4-dimethoxyaniline-5-sulfonicacid, 2-methoxy-5-methylaniline-4-sulfonic acid,4-aminoanisole-3-sulfonic acid, 4-aminotoluene-3-sulfonic acid,2-aminotoluene-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid,2-chloroaniline-5-sulfonic acid, 2-bromoaniline-4-sulfonic acid,2,6-dichloroaniline-4-sulfonic acid, 2,6-dimethylaniline-3-sulfonic acidor -4-sulfonic acid, 3-acetylamino-6-sulfoaniline,4-acetylamino-2-sulfoaniline, 1-aminonaphthalene-4-sulfonic acid,1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid,1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid,1-aminonaphthalene-3,7-disulfonic acid,1-aminonaphthalene-3,6,8-trisulfonic acid,1-aminonaphthalene-4,6,8-trisulfonic acid, 2-naphthylamine-5-sulfonicacid or -6- or -8-sulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonicacid, 2-aminonaphthalene-6,8-disulfonic acid,2-aminonaphthalene-1,6-disulfonic acid, 2-aminonaphthalene-1-sulfonicacid, 2-aminonaphthalene-1,5-disulfonic acid,2-aminonapthalene-3,6-disulfonic acid, 2-aminonaphthalene-4,8-disulfonicacid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-5-sulfonic acid,3-aminophenol-6-sulfonic acid, 4- or 5-nitro-2-aminophenol,4-nitro-6-sulfo-2-aminophenol, 1-hydroxy-2-aminonaphthalene-6,8- or-4,6-disulfonic acid, 6-nitro-2-hydroxy-4-sulfoaminonaphthalene,6-nitro-2-aminonaphthalene-4,8-disulfonic acid, 4-aminodiphenylene,4-amino-4'-methoxydiphenylamine,4-amino-4'-methoxydiphenylamine-3-sulfonic acid,4-(2'-methylphenylazo)-2-methylaniline, 4-aminoazobenzene,4'-nitrophenylazo-1-aminonaphthalene,4-(6'-sulfonaphthylazo)-1-aminonaphthalene,4-(2',5'-disulfophenylazo)-1-aminonaphthalene,4'-amino-3'-methyl-3-nitrobenzophenone, 4-amino-2-methylbenzophenone,2-amino-4'-methoxybenzophenone, 4-aminobenzophenone,4-(4'-aminophenylazo)-benzenesulfonic acid,4-(4'-amino-3'-methoxyphenylazo)-benzenesulfonic acid and2-ethoxy-1-aminonaphthalene-6-sulfonic acid.

Specific examples of aromatic diamines which do not possess afiber-reactive group, can be used as tetrazo components of thepreparation of the novel dyes and correspond to, for example, thegeneral formula (IV e) or (IV f) are 1,3-diaminobenzene,1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diamino-2-methylbenzene,1,4-diamino-2-methoxybenzene, 1,3-diamino-4-methylbenzene,1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methylbenzene,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diamino-4,8-disulfonaphthalene, 3,3'-diaminodiphenyl sulfone,4,4'-diaminodiphenyl sulfone, 3,3'-diaminodisulfodiphenyl sulfone,4,4'-diaminostilbene-2,2'-disulfonic acid, 2,7'-diaminodiphenyl sulfone,2,7'-diamino-4,5'-disulfodiphenyl sulfone, 4,4'-diaminobenzophenone,4,4'-diamino-3,3'-dinitrobenzophenone,3,3'-diamino-4,4'-dichlorobenzophenone, 4,4'- or 3,3'-diaminodiphenyl,4,4'-diamino-3,3'-dichlorodiphenyl, 4,4'-diamino-3,3'-dimethoxy- or-3,3'-dimethyl- or -2,2'-dimethyl- or -2,2'-dichloro- or-3,3'-diethoxydiphenyl, 4,4'-diamino-3,3'-dimethyl-6,6'-dinitrodiphenyl, 4,4'-diamino-2,2'- or -3,3'-disulfodiphenyl,4,4'-diamino-3,3'-dimethyl- or 3,3'-dimethoxy- or-2,2'-dimethoxy-6,6'-disulfodiphenyl,4,4'-diamino-2,2,',5,5'-tetrachlorodiphenyl,4,4'-diamino-3,3'-dinitrodiphenyl,4,4'-diamino-2,2'-dichloro-5,5'-dimethoxydiphenyl, 4,4'-diamino-2,2'- or-3,3'-dicarboxylic acid,4,4'-diamino-3,3'-dimethyldiphenyl-5,5'-disulfonic acid,4,4'-diamino-2-nitrodiphenyl, 4,4'-diamino-3-ethoxy- or-3-sulfodiphenyl, 4,4'-diamino-3,3'-dimethyl-5-sulfodiphenyl,4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane,4,4'-diamino-2,2',3,3'-tetramethyldiphenylmethane,4,4'-diaminodiphenylethane, 4,4'-diaminostilbene or4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid.

Aromatic radicals D of the diazo component of the aniline andaminonaphthalene series, which can carry a fiber-reactive radical, arederived from, for example, amines of the formulae V a-c ##STR10## whereR⁴, R⁵, p, x, Y and A have the above meanings.

Specific examples of aromatic compounds which carry a fiber-reactiveradical A and correspond to the formulae V a-c are derived from thefollowing diamines: 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonicacid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,3-diamino-4-methylbenzene, 1,4-diaminobenzene-2,6-disulfonic acid,1,5-diamino-4-methylbenzene-2-sulfonic acid,1,5-diamino-4-methoxybenzene-2-sulfonic acid,1,6-diamino-2-naphthol-4-sulfonic acid,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diamino-4,8-disulfonaphthalene,2,6-diamino-1-naphthol-4,8-disulfonic acid,1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methylbenzene,2,6-diaminophenol-4-sulfonic acid,5-(ω-aminomethyl)-2-aminonaphthalene-1-sulfonic acid,5-(ω-N-methylaminomethyl)-2-aminonaphthalene-1-sulfonic acid,4,4'-diaminostilbene-3,3'-dicarboxylic acid,4-(ω-N-methylaminomethyl)-aniline-2-sulfonic acid or3-(ω-N-methylaminomethyl)-aniline-6-sulfonic acid.

Preferred amines carrying fiber-reactive radicals A are the condensatesof 1,3- or 1,4-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonicacid, 2,6-diamino-4,8-disulfonaphthalene,5-(ω-aminomethyl)-2-aminonaphthalene-1-sulfonic acid or4-(ω-N-methylaminomethyl)aniline-2-sulfonic acid and, for example,cyanuric chloride or fluoride, as well as their condensates withammonia, primary or secondary aliphatic or aromatic amines, methanol,ethanol, isopropanol or phenol; furthermore, for example, acryloylchloride, β-chloropropionyl chloride, β-bromopropionyl chloride,chloroacetyl chloride, α,β-dichloropropionyl chloride,2,3-dichloroquinoxaline-5-carbonyl chloride,2,3-dichloroquinoxaline-6-carbonyl chloride, 2,3-dichloroquinazoline-5-or -6-sulfonyl chloride, 2,4-dichloroquinazoline-6- or -8-sulfonylchloride, 2,4,7- or 2,4,8-trichloroquinazoline-6-sulfonyl chloride,2,4-dichloroquinazoline-6-carbonyl chloride, 2,6-dichloropyrimidine-4-or -5-carbonyl chloride, 2,6dichloropyrimidine-5-sulfonyl chloride,2,4,6-trichloropyrimidine, 2,4,6-trichloro-5-methylpyrimidine,2,4,6-tribromo-5-cyanopyrimidine, 2,4,5,6-tetrachloropyrimidine,2,4,6-trifluoropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine,4,6-difluoro-5-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine,2-methylsulfonyl-4-chloropyrimidine-5-carbonyl chloride,2,4,6-trichloro-5-methylsulfonylpyrimidine,2,4,6-trifluoro-5-methylsulfonylpyrimidine,2-methyl-4,6-dichloro-5-methylsulfonylpyrimidine,2,4,5-trichloro-6-methylsulfonylpyrimidine,2,4,6-trichloropyrimidine-5-carbonyl chloride, tetrachloropyridazine,tetrafluoropyridazine, 3,6-dichloropyridazine-4-carbonyl chloride,p-(4,5-dichloropyridazinonyl)-benzoyl chloride,β-(4,5-dichloropyridazinonyl)-propionyl chloride,p-(4,5-dichloropyridazinonyl)-benzenesulfonyl chloride,p-(4,5-dichloropyridazinonyl)-benzenesulfonyl chloride,p-(4-fluoro-5-chloropyridazinonyl)-benzoyl chloride,p-(4-fluoro-5-chloropyridazinonyl)-benzenesulfonyl chloride,β-(4-fluoro-5-chloropyridazinonyl)-propionyl chloride and1,4-dichlorophthalazine-6-carbonyl chloride(pyridazinonyl=pyridazin-6-on-1-yl).

The radicals K of the coupling component are preferably derived from theaniline, naphthalene, pyrazole, pyridine, pyrimidine, indole,acylacetarylide or barbituric acid series, and may also carryfiber-reactive groups. They can therefore correspond to the formula

    --K(A).sub.p

where A, K and p have the above meanings.

Examples of coupling components of the aniline and naphthalene seriesare anilines, N-monosubstituted anilines, m-phenylenediaminederivatives, naphtholsulfonic acids, aminonaphthalenes, naphthols,hydroxynaphthoic acid derivatives, aminonaphthalenesulfonic acids andaminonaphtholsulfonic acids.

Coupling components which are derived from the aniline and naphthaleneseries and do not contain fiber-reactive groups are, for example,compounds of the formulae VI a-g ##STR11## where R⁶ is hydrogen or C₁-C₄ -alkyl, R⁷ is hydrogen or C₁ -C₄ -alkyl or is phenyl which can besubstituted by 1 or 2 substituents from the group comprising C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, chlorine, bromine and hydroxysulfonyl, R⁸ ishydrogen, or C₁ -C₄ -alkyl which can be substituted by hydroxyl, cyano,hydroxycarbonyl, hydroxysulfonyl, hydroxysulfonyloxy, methoxycarbonyl,ethoxycarbonyl or acetoxy, R⁹ is hydrogen or C₁ -C₄ -alkyl which can besubstituted by hydroxyl, cyano, hydroxycarbonyl, hydroxysulfonyl,hydroxysulfonyloxy, methoxycarbonyl, ethoxycarbonyl or acetoxy, or isbenzyl or is phenyl which can be substituted by C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, chlorine and/or hydroxysulfonyl, R¹⁰ is a C₁ -C₆ -alkylureidoor phenylureido group which can be substituted by chlorine, methyl,methoxy, nitro, hydroxysulfonyl and/or hydroxycarbonyl, or is a C₁ -C₆-alkylanoylamino, eg. acetylamino, propionylamino or cyclohexanoylamino,or a benzoylamino group which can be substituted by chlorine, methyl,methoxy, nitro, hydroxysulfonyl and/or hydroxycarbonyl, or is hydroxyl,R.sup. 11 is hydrogen or C₁ -C₆ -alkyl, in particular C₁ -C₄ -alkyl,which can be substituted by aryl, eg. phenyl, or by C₁ -C₄ -alkoxy,hydroxyl, phenoxy or C₁ -C₄ -alkanoyloxy, or is cycloalkyl, eg.cyclohexyl, or aryl, eg. phenyl, which can contain a hydroxysulfonylgroup, R¹² is hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine,bromine, acetylamino, amino, ureido, methylsulfonylamino,ethylsulfonylamino, dimethylaminosulfonylamino, methylamino, ethylamino,dimethylamino or diethylamino, R¹³ is hydrogen, methyl, ethyl, methoxy,ethoxy, chlorine or bromine, and p and m have the above meanings.

Specific examples are aniline-N-ω-methanesulfonic acid, o- andm-toluidine, o- and m-anisidine, cresidine, 2,5-dimethylaniline,2,5-dimethoxyaniline, m-aminoacetanilide, 3-amino-4-methoxyacetanilide,3-amino-4-methylacetanilide, m-aminophenylurea, N-methylaniline,N-methyl-m-toluidine, N-ethylaniline, N-ethyl-m-toluidine,N-β-hydroxyethylamine and N-β-hydroxy-m-toluidine.

Examples of naphtholsulfonic acids are 1-naphthol-3-sulfonic acid,1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid,1-naphthol-8-sulfonic acid, 1-naphthol-3,6-disulfonic acid,1-naphthol-3,8-disulfonic acid, 2-naphthol-5-sulfonic acid,2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid,2-naphthol-8-sulfonic acid, 2-naphthol-3,6-disulfonic acid,2-naphthol-6,8-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid,1,8-dihydroxynaphthalene-3,6-disulfonic acid,2,6-dihydroxynaphthalene-8-sulfonic acid and2,8-dihydroxynaphthalene-6-sulfonic acid.

Examples of further compounds are α-naphthylamine,N-phenyl-α-naphthylamine, N-ethyl-α-naphthylamine,N-phenyl-β-naphthylamine, 1,5-naphthylenediamine,1,8-naphthylenediamine, α-naphthol, β-naphthol,1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,2-hydroxynaphthalene-3-carboxylic acid N-phenylamide,2-hydroxynaphthalene-3-carboxylic acid N-(2'-methoxyphenyl)-amide and2-hydroxynaphthalene-3-carboxylic acid N-(2',5'-dimethoxyphenyl)amide.

Examples of aminonaphthalenesulfonic acids are1-naphthylamine-6-sulfonic acid, 1-naphthylamine-6/7-sulfonic acid,1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid,2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-5,7-disulfonic acidand 2-naphthylamine-6,8-disulfonic acid.

Examples of aminonaphtholsulfonic acids are1-amino-5-hydroxynaphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene-4-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-8-hydroxynaphthalene-4,6-disulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,1-acetylamino-8-hydroxynapthalene-3,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid and 2-(3'- and4'-sulfophenylamino)-8-hydroxynaphthalene-6-sulfonic acid. Of particularimportance are sulfo-containing and/or carboxyl-containing couplingcomponents which may or may not carry azo groups and which couple in theo- or p-position to a hydroxyl group and/or an amino group.

Examples of such coupling components are2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid,1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-benzoylamino-8-hydroxynapthalene-3,6-disulfonic acid,1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid or1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid.

Further examples of coupling components are, in particular,1-amino-8-hydroxynaphthalene-3,6- and -4,6-disulfonic acid and theirarylazo coupling products obtained by acidic coupling, of the formula##STR12## where D¹ can be a radical of a diazo component, for example aradical of the formula ##STR13## where R⁴, R⁵, p and m have the abovemeanings.

Specific radicals D¹ are derived from, for example, the followingamines: aniline, aniline-2-, -3- or -4-sulfonic acid, aniline-2,4-,-2,5- or -3,5-disulfonic acid, 2-naphthylamine-1,5- or -4,8-disulfonicacid, 2-naphthylamine-3,6,8- or -4,6,8-trisulfonic acid,1-naphthylamine-3,6,8- or -4,6,8-trisulfonic acid,1-naphthylamine-4-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 3- or4-aminoacetanilide, 4- or 5-acetylamino-2-sulfoaniline, 4-nitroaniline,4-nitroaniline-2-sulfonic acid or2-amino-6-acetylaminonaphthalene-4,8-disulfonic acid.

Examples of coupling components of other series are pyrazolones andaminopyrazoles, 2,6-diaminopyridines, pyridones, hydroxy- andaminopyrimidines, indoles, barbituric acid derivatives andacetoacetarylides.

Coupling components of these series which do not contain fiber-reactivegroups correspond to, for example, the formulae VII a-f ##STR14## whereT is a benzene or naphthalene nucleus, T¹ is C₁ -C₄ -alkyl, cyclohexylor benzyl or is phenyl which is monosubstituted or polysubstituted byfluorine, chlorine, bromine, methyl, methoxy, nitro, hydroxysulfonyl,hydroxycarbonyl, acetyl, acetylamino, methylsulfonyl, aminosulfonyl oraminocarbonyl, R14 is methyl, hydroxycarbonyl, methoxycarbonyl,ethoxycarbonyl or phenyl, R¹⁵ is hydrogen, methyl or ethyl or is C₁ -C₄-alkyl which is substituted by methoxy, ethoxy or cyano, R¹⁶ ishydrogen, methyl, sulfomethylene, hydroxysulfonyl, cyano oraminocarbonyl, R¹⁷ is hydrogen or C₁ -C₄ -alkyl which can be substitutedby phenyl or by sulfophenyl, or is C₁ -C₄ -alkyl which is substituted byhydroxyl, amino, methoxy, ethoxy, hydroxycarbonyl, hydroxysulfonyl,acetylamino, benzoylamino or cyano, or is cyclohexyl or phenyl or isphenyl which is substituted by hydroxycarbonyl, hydroxysulfonyl,benzoylamino, acetylamino, methyl, methoxy, cyano or chlorine or isamino which is substituted by phenyl, C₁ -C₄ -alkyl, acetyl or benzoyl,R¹⁸ is C₁ -C₄ -alkyl, phenyl, hydroxyl, cyano, acetyl, benzoyl,hydroxycarbonyl, methoxycarbonyl, aminocarbonyl or sulfomethylene, R¹⁹is hydrogen, chlorine, bromine, acetylamino, amino, nitro,hydroxysulfonyl, aminosulfonyl, methylsulfonyl, phenylsulfonyl,hydroxycarbonyl, methoxycarbonyl, acetyl, benzoyl, aminocarbonyl, cyanoor sulfomethylene, and R⁴, R⁵, R⁸, R⁹ and m have the above meanings.

Examples of pyrazolone coupling components are 3-methyl-, 3-carboxy- and3-alkoxycarbonyl-5-pyrazolones which can carry in the 1-positionhydrogen or phenyl which is unsubstituted or substituted by methyl,ethyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy, ethoxy,cyano, phenoxy, phenylsulfonyl, methylsulfonyl, hydroxysulfonyl,benzoyl, acetyl, acetylamino, nitro, hydroxyl, carboxyl, carbamyl orsulfamyl, or can carry hydroxysulfonyl-substituted α- or β-naphthyl, eg.1-phenyl-, 1-(2'-chlorophenyl)-, 1-(2'-methoxyphenyl)-,1-(2'-methylphenyl)-, 1-(2',5'-dichlorophenyl)-,1-(2',6'-dichlorophenyl)-, 1-(2'-methyl-6'-chlorophenyl)-,1-(2'-methoxy-5'-methylphenyl)-, 1-(2'-chloro-5'-sulfophenyl)-1-(2'-methoxy-5'-sulfophenyl)-, 1-(2'-methyl-4'-sulfophenyl)-,1-(2',5'-dichloro-4'-sulfophenyl)-, 1-(2',5'-disulfophenyl)-,1-(2'-carboxyphenyl)-, 1-(3'-sulfophenyl)-, 1-(4'-sulfophenyl)- or1-(3'-sulfamylphenyl)-3-carboxy-5-pyrazolone or 1-(3' - or4'-sulfophenyl)-, 1-(2'-chlorophenyl)-, 1-(2'-chloro-4'- or-5'-sulfophenyl)-, 1-(2'-methyl-4'-sulfophenyl)-,1-(2',5'-dichlorophenyl)-, 1-(4',8'-disulfo-β-naphthyl)- or1-(6'-sulfo-α-naphthyl)-3-methyl-5-pyrazolone, ethyl1-phenyl-5-pyrazolone-3-carboxylate, ethyl 5-pyrazolone-3-carboxylate or5-pyrazolone-3-carboxylic acid.

Examples of other coupling components derived from the pyrazole seriesare 1-methyl-, 1-ethyl-, 1-propyl-, 1-butyl-, 1-cyclohexyl-, 1-benzyl-and 1-phenyl-5-aminopyrazole, 1-(4'-chlorophenyl)- and1-(4'-methylphenyl)-5-aminopyrazole and1-phenyl-3-methyl-5-aminopyrazole.

Acetoacetanilides are, in particular, acetoacetanilide and itsderivatives which are monosubstituted or polysubstituted in the phenylnucleus by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino,hydroxylsulfonyl, hydroxycarbonyl, aminocarbonyl or aminosulfonyl.

Examples of coupling components derived from pyridine are thederivatives described in German Laid-Open Application DOS No. 2,260,827.

Examples of suitable pyrimidine coupling components are the compoundslisted in German Laid-Open Applications DOS NO. 2,202,820, DOS No.2,308,663 and DOS No. 3,119,349. Barbituric acid and its N-substitutionproducts may also be mentioned. N-Substituents are, in particular, C₁-C₄ -alkyl and unsubstituted or substituted phenyl.

Examples of indole coupling components are 2-methylindole,2-phenylindole, 2-phenylindole-5-sulfonic acid, 1-methyl-2-phenylindoleand 1-(2'-hydroxyethyl)-, 1-(2'-carboxyethyl)- and1-(2'-carbamylethyl)-2-methylindole and -2-phenylindole.

Examples of pyridone coupling components are1-ethyl-2-hydroxy-4-methyl-5-carboxamidopyrid-6-one,1-(2'-hydroxyethyl)-2-hydroxy-4-methyl-5-carboxamidopyrid-6-one,1-phenyl-2-hydroxy-4-methyl-5-carboxamidopyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-ethyl-2-hydroxy-4-sulfomethyl-5-carboxamidopyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-sulfomethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-methylhydroxy-5-acetylpyrid-6-one,1,4-dimethyl-2-hydroxy-5-cyanopyrid-6-one,1,4-dimethylhydroxy-5-carboxamidopyrid-6-one,2,6-dihydroxy-4-ethyl-5-cyanopyridine,2,6-dihydroxy-4-ethyl-5-carboxamidopyridine,1-ethyl-2-hydroxy-4-methyl-5-sulfomethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-methylsulfonylpyrid-6-one and1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonylpyrid-6-one.

Examples of coupling components which are derived from the aniline andnaphthalene series and contain fiber-reactive groups are compounds ofthe formulae VIII a-e ##STR15## where R⁶, R⁷, R⁸, R⁹, A and p have theabove meanings.

Particularly important compounds among these are sulfo-containing and/orcarboxyl-containing coupling components which may or may not carry azogroups, which couple in the o- or p-position to a hydroxyl group and/oran amino group and which carry a fiber-reactive radical A, eg.2-(5'-hydroxy-7'-sulfonaphth-2'-ylamino)-4,6-dichlorotriazine,2-(5'-hydroxy-7'-sulfonaphth-2-ylmethylamino)-4,6-dichlorotriazine,2-(8'-hydroxy-6'-sulfonaphth-2'-ylamino)-4,6-dichlorotriazine,2-(8'-hydroxy-6'-sulfonaphth-2'-yl-methylamino)-4,6-dichlorotriazine,2-(8'-hydroxy-3',6'-disulfonaphth-1'-ylamino)-4,6-dichlorotriazine or2-(8'-hydroxy-4',6'-disulfonaphth-1'-ylamino)-4,6-dichlorotriazine, ortheir monocondensates with primary and secondary, aliphatic and aromaticamines, such as ammonia, methylamine, ethylamine, taurine, glycine,sarcosine, β-hydroxyethylamine, dihydroxyethylamine, hydrazine, aniline,N-methylaniline, N-ethylaniline, morpholine, toluidine, anisidine,cresidine, o-, m- or p-anilinesulfonic acid, aniline-2,4- or-2,5-disulfonic acid, o-, m- or p-aminobenzoic acid, m- orp-vinylsulfonylaniline, m- or p-sulfatoethylsulfonylaniline,N-methylanthranilic acid or m- or p-allylsulfonylaniline.

Further examples are the secondary condensates of1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid or2-methylamino-5-hydroxynaphthalene-7-sulfonic acid with cyanuricfluoride or a primary or secondary aliphatic or aromatic amine.

Other examples are the monocondensates of1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid or2-methylamino-5-hydroxynaphthalene-7-sulfonic acid with, for example,acryloyl chloride, β-chloropropionyl chloride, β-bromopropionylchloride, chloroacetyl chloride, α,β-dichloropropionyl chloride,2,3-dichloroquinoxaline-5-carbonyl chloride,2,3-dichloroquinoxaline-6-carbonyl chloride, 2,3-dichloroquinazoline-5-or -6-sulfonyl chloride, 2,4-dichloroquinazoline-6- or -7-sulfonylchloride, 2,4,6-trichloroquinoazoline-7- or -8-sulfonyl chloride, 2,4,7-or 2,4,8-trichloroquinazoline-6-sulfonyl chloride,2,4-dichloroquinazoline-6-carbonyl chloride, 2,6-dichloropyrimidine-4-or -5-carbonyl chloride, 2,6-dichloropyrimidine-5-sulfonyl chloride,2,4,6-trichloropyrimidine, 2,4,6-trichloro-5-methylpyrimidine,2,4,6-tribromo-5-cyanopyrimidine, 2,4,5,6-tetrachloropyrimidine,2,4,6-trifluoropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine,4,6-difluoro-5-chloropyrimidine,2-methylsulfonyl-4-chloro-6-methylpyrimidine,2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine,2-methylsulfonyl-4-chloropyrimidine-5-carbonyl chloride,2,4,6-trichloro-5-methylsulfonylpyrimidine,2,4,6-trifluoro-5-methylsulfonylpyrmidine,2-methyl-4,6-dichloro-5-methylsulfonylpyrimidine,2,4,5-trichloro-6-methylsulfonylpyrimidine,2,4,6-trichloropyrimidine-5-carbonyl chloride, tetrachloropyridazine,tetrafluoropyridazine, 3,6-dichloropyridazine-4-carbonyl chloride,p-(4,5-dichloropyridazinonyl)-benzoyl chloride,β-(4,5-dichloropyridazinonyl)-propionyl chloride,p-(4,5-dichloropyridazinonyl)-benzenesulfonyl chloride,p-(4-fluoro-5-chloropyridazinonyl)-benzoyl chloride,p-(4-fluoro-5-chloropyridazinonyl)-benzenesulfonyl chloride,β-(4-fluoro-5-chloropyridazinonyl)-propionyl chloride and1,4-dichloro-phthalazine-6-carbonyl chloride(pyridazinonyl=pyridazin-6-on-1-yl).

Other examples are, in particular, the arylazo coupling products,obtained by acidic coupling, of the 1-amino-8-hydroxynaphthalene-3,6- or-4,6-disulfonic acid of the formula ##STR16## where D² can be a diazocomponent radical which contains reactive groups, for example a radicalof the formula ##STR17## where R⁴, R⁵, x, p and A have the abovemeanings.

Specific examples of aromatic amines from which the diazo componentradicals D² which carry fiber-reactive radicals A are derived are:1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,3-diamino-4-methylbenzene, 1,4-diaminobenzene-2,6-disulfonic acid,1,5-diamino-4-methylbenzene-2-sulfonic acid,1,5-diamino-4-methoxybenzene-2-sulfonic acid,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diamino-4,8-disulfonaphthalene, 1,3-diaminobenzene-5-sulfonic acid,1,3-diamino-5-methylbenzene,5-(ω-aminomethyl)-2-aminonaphthalene-1-sulfonic acid,5-(ω-N-methylaminomethyl)-2-aminonaphthalene-1-sulfonic acid,4,4'-diaminostilbene-3,3'-dicarboxylic acid,4-(ω-N-methylaminomethyl)-aniline-2-sulfonic acid and3-(ω-N-methylaminomethyl)-aniline-6-sulfonic acid, and in all theseamino compounds the single primary or secondary amino group issubstituted by a fiber-reactive acyl radical A.

Specific examples of the diazo component radicals D² which carryfiber-reactive groups are ##STR18##

Coupling components which are derived from the pyrazolone,aminopyrazole, 2,6-diaminopyridine, pyridone, hydroxypyrimidine,aminopyrimidine, indole, barbituric acid or acetoacetarylide series andcontain fiber-reactive groups correspond to, for example, the formulaeIX a-f ##STR19## where T² is a benzene or naphthalene nucleus, R²⁰ is C₁-C₄ -alkyl, benzyl, phenylethyl or phenyl, and the phenyl nuclei can befurther substituted by fluorine, chlorine, bromine, methyl, methoxy,cyano, hydroxysulfonyl, hydroxycarbonyl, acetyl, nitro, aminocarbonyl oraminosulfonyl, and R¹, R⁴, R⁵, R⁸, R⁹, R¹⁵, R¹⁶, R¹⁸, R¹⁹, p an A havethe above meanings.

Pyrazolone coupling components which carry fiber-reactive radicals A arederived from, for example, one of the following pyrazolones: 1-(3'- or4'-aminophenyl)-, 1-(2'-sulfo-5'-aminophenyl)- or1-(2'-methoxy-5'-aminophenyl)-3-carboxypyrazol-5-one, 1-(3'- or4'-aminophenyl)- or 1-(3'- or 4'-nitrophenyl)-3-methylpyrazol-5-one or1-(3'- or 4'-nitrophenyl)-, 1-(6'-nitro-4',8'-disulfonaphth-2'-yl)- or1-(6'-amino-4',8'-disulfonaphth-2'-yl)-3-carboxypyrazol-5-one.

Specific examples of pyrazolones which carry fiber-reactive radicals Aare: ##STR20##

Further examples are: ##STR21##

Specific examples of pyridones which carry fiber-reactive radicals Aare: ##STR22##

Radicals of the formula ##STR23## and their preparation are described inPatent Application P No. 32 29 325.9. For bonding the dye radicals X,any method conventionally used in the chemistry of reactive dyes can beemployed. A representative selection of preparation methods for the dyesof the formula I is described in the Examples, in which parts andpercentages are by weight, unless stated otherwise.

Of particular industrial importance are compounds of the general formula##STR24## where D³ and D⁴ are identical or different radicals of diazocomponents, one or both of these carrying a radical of the formula##STR25##

Other useful compounds are those of the formula ##STR26## where Q is anacyl radical which may or may not contain a reactive radical, and D³, pand R⁸ have the above meanings.

Dye radicals X of the dioxazine series correspond to the general formula##STR27## where L¹ and L² independently of one another are eachhydrogen, chlorine, bromine, cyano, unsubstituted or substituted alkyl,aryl, hetaryl, alkoxy, aryloxy or acylamino, and the groups L³independently of one another are each a radical of the formula ##STR28##where e¹ is 0, 1 or 2, L⁴ is a bridge member, L⁵ is hydrogen, alkoxy oracylamino, and L⁶ is hydrogen or C₁ -C₄ -alkyl.

Specific examples of radicals L¹ and L², in addition to those statedabove, are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₆ H₅, C₆ H₄ Cl, C₆ H₃ Cl₂, C₆ H₄CH₃, C₆ H₄ OCH₃, C₆ H₄ NO₂, C₆ H₃ ClCH₃, 2-thienyl, OCH₃, OC₂ H₅, OC₃H₇, OC₄ H₉, OC₆ H₅, OC₆ H₄ Cl, OC₆ H₄ CH₃, NHCOCH₃, NHCOC₂ H₅ and NHCOC₃H₇.

L¹ and L² are each preferably hydrogen or, in particular, Cl.

Specific examples of radicals L⁵ are hydrogen, methoxy, ethoxy, propoxy,butoxy, acetylamino, propionylamino and butyrylamino.

L⁵ is preferably hydrogen, methoxy or acetylamino.

Examples of bridge members L⁴ are sulfonyl, --NH--(alkylene)--NH--,--SO₂ --NH--(alkylene)--NH--, --NH--(arylene)--NH--, --SO₂--NH--(arylene)--NH--, --NH--(alkylene)--O--(alkylene)--NH--, --SO₂--(alkylene)--O--(alkylene)--NH--, --O--(alkylene)--O--(arylene)--NH--,--NH--(alkylene)--NH--(arylene)--NH--, --NH--(aralkylene)--NH--, --SO₂--NH--(aralkylene)--NH--, --CH₂ --NH-- and --CH₂--NHCO--(alkylene)--NH--, and the hydrogen in the NH groups can bereplaced by unsubstituted or substituted alkyl, cycloalkyl or arylgroups, which may furthermore be bonded to one another to form aheterocyclic ring.

Specific examples of radicals L⁴ are ##STR29##

Examples of preferred radicals L⁴ are: ##STR30##

Anthraquinone radicals X are of, for example, the formula ##STR31##where 1 is 0 or 1 and L⁹ is a direct bond or a bridge member.

Examples of bridge members are iminophenylene, iminoalkylene,iminocycloalkylene and iminoheteroarylene which are unsubstituted ormonosubstituted or polysubstituted by CH₃, SO₃ H, SO₂ NH₂, Cl, Br orOCH₃, or polynuclear radicals which contain a further reactive group.

Specific examples of bridge members L⁹ are: ##STR32##

Examples of preferred bridge members L⁹ are: ##STR33##

Phthalocyanine radicals X are of the formula ##STR34## where Me isnickel or copper, L⁷ and L⁸ independently of one another are eachhydrogen or unsubstituted or substituted alkyl, aralkyl or aryl, and L¹⁰is a bridge member or a direct bond.

Specific examples of radicals L⁷ and L⁸, in addition to hydrogen, aremethyl, ethyl, propyl, butyl, hydroxyethyl and hydroxypropyl. Examplesof bridge members L¹⁰ are --HN--(alkylene)--NH--,--HN--(cycloalkylene)--NH--, --NH--aralkylene--NH--,--NH--(arylene)--NH--, --NH--(arylene)--N═N--(hetarylene)--NH,--NH--(hetarylene)--N═N--(arylene)--NH-- and--NH--(arylene)--N═N--(arylene)--NH, and the hydrogen atoms of the NHgroups can be replaced by unsubstituted or substituted alkyl, cycloalkylor aryl groups, which may furthermore be bonded to one another and mayhence form a heterocyclic ring.

Specific examples of bridge members L¹⁰ are: ##STR35##

Examples of preferred bridge members L¹⁰ are: ##STR36##

Instead of the azo dye radicals X, it is also possible for dyes of theformula I to contain the corresponding metal complex dye radicals;particularly suitable complex-forming metals are copper, cobalt,chromium, nickel and iron, the three first-mentioned metals beingpreferred.

As a rule, the metals are bonded to the dye molecules via --O-- or--COO--.

The Co and Cr complexes are 1:2 complexes, whereas when Cu is used, 1:1complexes are obtained exclusively.

Met is preferably copper, cobalt or chromium. The types of dyesmentioned below can furthermore be substituted by substituentsconventionally found in reactive dyes, eg. Cl, Br, OCH₃, NHCONH₂, NO₂,SO₃ H, SO₂ NH₂, COOH or CONH₂. The dyes are synthesized by aconventional method.

Examples of preferred types of complexes are: ##STR37##

In the above formula, aryl is a phenyl or naphthyl radical which issubstituted by any desired substituents, in particular by SO₃ H, Cl orOCH₃, and L⁹ has the above meanings.

It is also possible to prepare asymmetric 1:2 Co or Cr metal complexes,for example ##STR38##

Particularly brilliant blue dyes are obtained in the series comprisingthe copper formazane complex dyes. Here, formazane radicals X are of thegeneral formula ##STR39## where Ar has the meanings stated on page 46.

The compounds of the formula I are useful for dyeing hydroxyl-containingsubstrates, wool and nylons, and, depending on their constitution, giveyellow to blue dyeings which are generally distinguished by good yieldand good fastness properties, such as wetfastness and lightfastness.Examples of substrates are, in particular, cotton and wool.

Any conventional dyeing method can be used, depending on the reactiveradical.

The Examples in the Tables below describe novel dyes of the generalformula I, the abbreviations A¹ to A⁶ having the following meanings:

EXAMPLE 1

14.2 parts of 1-(4'-sulfophenyl)-3-carboxypyrazol-5-one are added to asuspension of 16 parts of the product obtained by diazotizing1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in anaqueous solution containing hydrochloric acid. The pH is brought to 6-7by sprinkling in 25 parts of trisodium phosphate. When the coupling iscomplete, the dye formed is precipitated with 70 parts of sodiumchloride, and is dried under mild conditions. It dyes cotton in greenishyellow lightfast hues.

The dye described in Example 1 is of the formula ##STR41##

Other dyes according to the invention are listed in Table 1 where columnI shows the radical of the diazo component used, which has one of thestated meanings A⁷ or A⁸, column II indicates the coupling componentused instead of 1-(4'-sulfophenyl)-3-carboxypyrazol-5-one, and columnIII gives the hue obtained on dyeing cotton.

                  TABLE 1    ______________________________________    I     II                        III    ______________________________________     2  A.sup.8              1-(2'-Methyl-4'-sulfophenyl)-3-carboxy-                                        greenish              pyrazol-5-one             yellow     3  "     1-(2',4'-Disulfophenyl)-3-methylpyrazol-5-one                                        greenish                                        yellow     4  "     1-(2'-Chloro-5'-sulfophenyl)-3-methyl-                                        greenish              pyrazol-5-one             yellow     5  "     4,6-Dihydroxy-6-morpholinopyrimidine                                        greenish                                        yellow     6  "     4-Amino-6-hydroxy-2-morpholinopyrimidine                                        yellow     7  "     1-Ethyl-2-hydroxy-4-methyl-5-sulfomethyl-                                        yellow              pyrid-6-one     8  "     5-Aminocarbonyl-1-ethyl-2-hydroxy-4-                                        yellow              methylpyrid-6-one     9  A.sup.7              1-Hydroxynaphthalene-3,6-disulfonic acid                                        yellow-                                        ish red    10  "     1-Hydroxynaphthalene-3,8-disulfonic acid                                        yellow-                                        ish red    11  "     1-Hydroxynaphthalene-4,8-disulfonic acid                                        yellow-                                        ish red    12  "     1-Hydroxynaphthalene-3,6,8-trisulfonic acid                                        yellow-                                        ish red    13  A.sup.8              1-(4'-sulfophenyl)-3-carboxypyrazol-5-one                                        yellow    14  "     1-Hydroxynaphthalene-4-sulfonic acid                                        red    15  "     1-Hydroxynaphthalene-3,6-disulfonic acid                                        red    16  "     1-Hydroxynaphthalene-3,8-disulfonic acid                                        red    17  "     1-Hydroxynaphthalene-4,8-disulfonic acid                                        red    18  "     1-Hydroxynaphthalene-3,6,8-trisulfonic acid                                        red    ______________________________________

EXAMPLE 19

39 parts of 1-butyrylamino-8-hydroxynaphthalene-4,6-disulfonic acid aredissolved in 500 parts of water at 0° C. to give a neutral solution, and32 parts of the product obtained by diazotizing1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added. Coupling is carried outwith the addition of 10.5 parts of sodium bicarbonate at pH 5-6, and thedye is precipitated with potassium chloride. The pressed material isfreeze-dried. The resulting dark red powder dyes cotton in brilliant redlightfast hues.

The dye described in Example 19 is of the formula ##STR42##

Other dyes according to the invention are summarized in Table 2, wherecolumn I shows the radical of the diazo component used, whichcorresponds to the abbreviation A⁷ or A⁸, column II indicates thecoupling component used, and column III gives the hue obtained oncotton.

                  TABLE 2    ______________________________________    Ex-    am-    ple  I     II                       III    ______________________________________    20   A.sup.7               1-Acetylamino-8-hydroxynaphthalene-                                        red               3,6-disulfonic acid    21   "     1-Benzoylamino-8-hydroxynaphthalene-4,6-                                        yellowish               disulfonic acid          red    22   "     1-Butyrylamino-8-hydroxynaphthalene-3,6-                                        red               disulfonic acid    23   "     1-(3'-Sulfopropionylamino)-8-hydroxynaph-                                        yellowish               thalene-3,6-disulfonic acid                                        red    24   "     1-(2'-Sulfobenzoylamino)-8-hydroxynaphtha-                                        yellowish               lene-3,6-disulfonic acid red    25   A.sup.8               1-(3'-Sulfopropionylamino)-8-hydroxy-                                        bluish               naphthalene-4,6-disulfonic acid                                        red    26   "     1-(2'-Carboxybenzoylamino)-8-hydroxy-                                        bluish               naphthalene-4,6-disulfonic acid                                        red    27   "     1-Benzoylamino-8-hydroxynaphthalene-3,6-                                        bluish               disulfonic acid          red    28   "     1-(Cyclohexylaminocarbonylamino)-8-                                        bluish               hydroxynaphthalene-3,6-  red               disulfonic acid    29   A.sup.7               2-(3'-Sulfopropionylamino)-5-hydroxy-                                        orange               naphthalene-7-sulfonic acid    30   "     2-(3'-Sulfopropionylamino)-8-hydroxy-                                        yellowish               naphthalene-6-sulfonic acid                                        red    31   "     2-(2'-Sulfobenzoylamino)-8-hydroxynaphtha-                                        yellowish               lene-6-sulfonic acid     red    32   "     2-(Sulfomethylamino)-8-hydroxynaphtha-                                        red               lene-6-sulfonic acid    33   A.sup.8               2-(3'-Sulfophenylamino)-8-hydroxynaphtha-                                        brown               lene-6-sulfonic acid    ______________________________________

EXAMPLE 34

25.3 parts of aniline-2,5-disulfonic acid are diazotized in a solutioncontaining hydrochloric acid, after which a suspension of 31.6 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 300 parts of wateris added dropwise. Coupling is carried out overnight in a solutionhaving a high concentration of hydrochloric acid. Thereafter, 32 partsof the product obtained by diazotizing1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added at 5° C., and themixture is stirred for 3 hours at pH 6.5-7, while adding 18.8 parts ofsodium carbonate. The dye is precipitated from the neutral solution withsodium chloride, and is dried under mild conditions. The resulting blackpowder dyes cotton in greenish navy lightfast hues.

The dye described in Example 34 is of the formula ##STR43##

Other dyes according to the invention are summarized in Table 3, wherecolumn I shows the radical of the diazo component coupled in an acidicmedium, column II indicates the radical of the diazo component coupledin a neutral or alkaline medium, and column III lists the hue obtainedon cotton.

                  TABLE 3    ______________________________________    Ex-    am-    ple  I              II              III    ______________________________________    35   4-Sulfophenyl  A.sup.8         greenish                                        navy    36   1,5-Disulfonaphth-                        "               greenish         2-yl                           navy    37   3,6,8-Trisulfo-                        "               greenish         naphth-2-yl                    navy    38   2-Sulfo-5-(4',6'-                        "               greenish         dichlorotriazinyl)-            navy         aminophenyl    39   4-(2'-Sulfatoethyl-                        "               navy         sulfonyl)-phenyl    40   A.sup.8        4-Sulfophenyl   navy    41   "              1,5-Disulfonaphth-2-yl                                        navy    42   "              2,5-Disulfophenyl                                        navy    43   "              3,6,8-Trisulfonaphth-2-yl                                        navy    44   "              2-Sulfo-5-(4',6'-dichloro-                                        navy                        triazinyl)-aminophenyl    45   "              4-(2'-Sulfatoethylsul-                                        navy                        fonyl)-phenyl    46   "              4-(2'-Sulfatoethylamino-                                        navy                        sulfonyl)-phenyl    47   "              A.sup.8         navy         A.sup.7        A.sup.7         reddish                                        navy    49   "              A.sup.8         navy    50   "              4-Sulfophenyl   navy    51   "              2,5-Disulfophenyl                                        navy    52   "              1,5-Disulfonaphth-2-yl                                        navy    53   "              4-Aminosulfophenyl                                        navy    54   "              2-Sulfo-5-(4',6'-dichloro-                                        reddish                        triazinyl)-aminophenyl                                        navy    55   "              2-Sulfo-5-[4'-(4"-sulfo-                                        reddish                        phenylamino)-6'-chloro-                                        navy                        triazinyl]-aminophenyl    56   "              2-Sulfo-5-(4'-methoxy-                                        navy                        6'-chlorotriazinyl)-                        aminophenyl    57   "              4-(2'-Sulfatoethylsul-                                        navy                        fonyl)-phenyl    58   "              4-(2'-Sulfatoethylamino-                                        navy                        sulfonyl)-phenyl    59   4-Allylsulfonyl-                        A.sup.7         navy         phenyl    60   4-Aminosulfonyl-                        "               navy         phenyl    61   2-Sulfo-5-(4',6'-                        "               navy         dichlorotriazinyl)-         aminophenyl    62   2-Sulfo-5-(4'- "               navy         methoxy-6'-chloro-         triazinyl)-amino-         phenyl    63   2-Sulfo-5-[4'-(2"-                        "               navy         methylphenylamino)-         6'-fluorotriazinyl]-         aminophenyl    64   4-Sulfophenyl  "               navy    65   1,5-Disulfonaphth-                        "               navy         2-yl    66   3,6,8-Trisulfo-                        "               navy         naphth-2-yl    67   4-(2'-Sulfatoethyl-                        "               navy         aminosulfonyl)-         phenyl    68   2-Chloro-4,6-disul-                        A.sup.8         navy         fophenyl    69   2-Methyl-4,6-disul-                        A.sup.7         navy         fophenyl    70   A.sup.7        2-Sulfo-5-[4'-(2"-methyl-                                        navy                        phenylamino)-6'-fluoro-                        triazinyl]-aminophenyl    ______________________________________

EXAMPLE 71

61 parts of the secondary condensate obtained fromaniline-2,5-disulfonic acid, cyanuric chloride and2-amino-5-hydroxynaphthalene-7-sulfonic acid are dissolved in 800 partsof water to give a neutral solution, and 32 parts of the productobtained by diazotizing1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added at 0° C. Coupling iscompleted in a slightly acidic medium, with the addition of 14.6 partsof sodium bicarbonate, and the dye is prrecipitated by adding sodiumchloride. The pressed material is dried under mild conditions. Theresulting orange brown powder dyes cotton in brilliant orange hues. Thedye is of the formula ##STR44##

EXAMPLE 72

32 parts of the product obtained by diazotizing1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are introduced into a neutralsolution, in 800 parts of water, of 46.7 parts of the primary condensateobtained from cyanuric chloride and1-amino-8-hydroxynaphthalene-4,6-disulfonic acid. 23.5 parts oftrisodium phosphate are added during the coupling, and the dye isisolated by adding sodium chloride. The pressed material isfreeze-dried. An aqueous solution of the resulting red powder dyescotton in brilliant yellowish red lightfast hues. The dye is of theformula ##STR45##

EXAMPLE 73

58.7 parts of the secondary condensate obtained from aniline-4-sulfonicacid, cyanuric fluoride and 1-amino-8-hydroxynaphthalene-3,6-disulfonicacid are dissolved in 800 parts of water at 0° C. to give a neutralsolution, and 32 parts of the product obtained by diazotizing1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added. Coupling is completedin a slightly acidic medium by adding 24.5 parts of trisodium phosphate,and the dye is precipitated with sodium chloride and then dried. Anaqueous solution of the resulting red powder dyes cotton in brilliantred fast hues. The dye is of the formula ##STR46##

EXAMPLE 74

71.2 parts of the secondary condensate obtained from4-(2'-sulfatoethylsulfonyl)-aniline, cyanuric chloride and1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 800parts of water at 5° C. and 32 parts of the product obtained bydiazotizing 1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-onein a solution containing hydrochloric acid are added. The pH is keptslightly acidic during the coupling by adding 18.4 parts of sodiumbicarbonate. The dye is precipitated by adding sodium chloride, and isfreeze-dried. An aqueous solution of the resulting blackish red powderdyes cotton in dull bluish red hues. The dye is of the formula ##STR47##

Further dyes according to the invention are listed in Table 4, wherecolumn I shows the radical of the diazo component used, column IIindicates the coupling component used, column III gives the primarytriazine condensate used, and column IV lists the hue obtained oncotton.

                  TABLE 4    ______________________________________    Ex-    ample I     II            III         IV    ______________________________________    75    A.sup.7                1-Amino-8-hydroxy-                              2-Methoxy-4,6-di-                                          red                naphthalene-3,6-                              chlorotriazine                disulfonic acid    76    A.sup.7                1-Amino-8-hydroxy-                              2-(4'-Sulfophenyl-                                          red                naphthalene-3,6-                              amino)-4,6-dichloro-                disulfonic acid                              triazine    77    A.sup.7                1-Amino-8-hydroxy-                              2-(2',5'-Disulfo-                                          red                naphthalene-3,6-                              phenylamino)-4,6-di-                disulfonic acid                              chlorotriazine    78    A.sup.7                1-(2'-Sulfo-4'-                              2-(3'-Sulfophenyl-                                          yellow                aminophenyl)-3-                              amino)-4,6-dichloro-                carboxypyrazol-                              triazine                5-one    79    A.sup.7                1-Aminoethyl-5-                              2-(2',5'-Disulfo-                                          greenish                aminocarbonyl-4-                              phenylamino)-4,6-di-                                          yellow                methyl-6-hydroxy-                              chlorotriazine                pyrid-2-one    80    A.sup.8                1-(2'-Sulfo-4'-                              2-(4'-Sulfophenyl-                                          yellow                aminophenyl)- amino)-4,6-trichloro-                3-carboxypyra-                              triazine                zol-5-one    ______________________________________

EXAMPLE 81

63 parts of the dye obtained by coupling diazotized2-amino-4-(4',6'-dichloro-1',3',5'-triazinyl)-aminobezenesulfonic acidto 1-(4'-sulfophenyl)-3-carboxypyrazol-5-one are dissolved in 950 partsof water, 24 parts of1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one are added, and themixture is stirred for 4 hours at 35° C., the pH being maintained at 6.5by the addition of 2N sodium carbonate solution. When the reaction iscomplete, the dye is precipitated with sodium chloride, and is driedunder mild conditions. It dyes cotton in greenish yellow fast hues, andis of the formula ##STR48##

EXAMPLE 82

54.9 parts of the sodium salt of the dye, obtained by coupling2-amino-5-acetylaminobenzenesulfonic acid to1-(4'-sulfophenyl)-3-carboxypyrazol-5-one and then hydrolyzing theacetylamino group, are dissolved in 750 parts of ice water, and reactedwith 18.5 parts of cyanuric chloride at pH 6. When diazotizable aminogroups are no longer detectable, 24 parts of1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one are added, and themixture is stirred for 4 hours at 30° C. and pH 6.5. The dye isprecipitated with potassium chloride, and dried under mild conditions.It gives brilliant reddish yellow dyeings on cotton, and is of theformula ##STR49##

EXAMPLE 83

36.1 parts of 1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid in300 parts of water are added, at 5° C., to a suspension of 33.6 parts ofthe product obtained by diazotizing, in a solution containinghydrochloric acid, the primary condensate of cyanuric chloride and1,3-phenylenediamine-4-sulfonic acid. Coupling is carried out at pH 5,with the addition of 17.9 parts of sodium bicarbonate. 23.9 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 100 parts ofdimethylformamide are added, and condensation is carried out at 35°-40°C. and at pH 6, 14.9 parts of sodium bicarbonate being added. Theprecipitated dye is filtered off under suction and dried. The resultingred powder dyes cotton in brilliant yellowish red lightfast hues. It isof the formula ##STR50##

Further dyes according to the invention are listed in Table 5, wherecolumn I shows the type of the halogen atom which can be split off inthe triazine radical, column II indicates the radical of the amine usedinstead of 1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one, columnsIII and IV show the compounds used instead of1,3-phenylenediamine-4-sulfonic acid and1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid respectively, andcolumn V indicates the hue obtained on cotton.

                                      TABLE 5    __________________________________________________________________________    Example         I II             III         IV           V    __________________________________________________________________________     84  Cl           A.sup.1             1,3-Phenylenediamine-                         1-Benzoylamino-8-                                      red             4,6-disulfonic acid                         hydroxynaphthalene-                         3,6-disulfonic acid     85  Cl           A.sup.2             1,3-Phenylenediamine-                         1-(2'-Sulfobenzoyl-                                      red             4-sulfonic acid                         amino)-8-hydroxy-                         naphthalene-3,6-                         disulfonic acid     86  Cl           A.sup.2             1,3-Phenylenediamine-                         1-(3'-Carboxypro-                                      yellowish             4-sulfonic acid                         pionylamino)-8-                                      red                         hydroxynaphthalene-                         4,6-disulfonic acid     87  F A.sup.2             1,3-Phenylenediamine-                         1-(3'-Sulfopropi-                                      red             4-sulfonic acid                         onylamino)-8-hyd-                         roxynaphthalene-3,6-                         disulfonic acid     88  F A.sup.1             1,3-Phenylenediamine-                         1-Acetylamino-8-                                      yellowish             4-sulfonic acid                         hydroxynaphthalene-                                      red                         4,6-disulfonic acid     89  Cl           A.sup.1             1,3-Phenylenediamine-                         2-(3'-Sulfopropi-                                      orange             4-sulfonic acid                         onylamino)-5-hyd-                         roxynaphthalene-7-                         sulfonic acid     90  Cl           A.sup.1             1,3-Phenylenediamine-                         2-(Sulfoacetyl-                                      orange             4-sulfonic acid                         amino)-5-hydroxynaph-                         thalene-7-sulfonic                         acid     91  Cl           A.sup.2             1,3-Phenylenediamine-                         2-(2'-Sulfobenzoyl-                                      orange             4,6-disulfonic acid                         amino)-5-hydroxynaph-                         thalene-7-sulfonic                         acid     92  F A.sup.2             1,3-Phenylenediamine-                         2-(Sulfoacetyl-                                      orange             4-sulfonic acid                         amino)-5-hydroxynaph-                         thalene-7-sulfonic                         acid     93  Cl           A.sup.2             1,3-Phenylenediamine-                         2-(3'-Sulfopropi-                                      yellowish             4-sulfonic acid                         onylamino)-8-                                      red                         hydroxynaphthalene-                         6-sulfonic acid     94  Cl           A.sup.1             1,3-Phenylenediamine-                         2-(2'-Sulfobenzoyl-                                      yellowish             4,6-disulfonic acid                         amino)-8-hydroxynaph-                                      red                         thalene-6-sulfonic                         acid     95  Cl           A.sup.1             1,3-Phenylenediamine-                         2-(Sulfomethyl-                                      bluish             4-sulfonic acid                         amino)-8-hydroxy-                                      red                         naphthalene-6-sul-                         fonic acid     96  Cl           A.sup.1             1,3-Phenylenediamine-                         2-[3'-(2"-carboxy-                                      orange             4,6-disulfonic acid                         ethoxy)-propionylami-                         no]-5-hydroxynaph-                         thalene-7-sulfonic                         acid     97  Cl           A.sup.2             1,3-Phenylenediamine-                         1-[4'-chloro-6'-                                      red             4-sulfonic acid                         (2",5"-disulfo-1"-                         phenylamino)-tri-                         azinylamino]-8-                         hydroxynaphthalene-                         3,6-disulfonic acid     98  Cl           A.sup.2             1,3-Phenylenediamine-                         1-[4'-Chloro-6'-(4"-                                      red             4-sulfonic acid                         sulfo-1"-phenyl-                         amino)-triazinyl-                         amino]-8-hydroxy-                         naphthalene-3,6-                         disulfonic acid     99  Cl           A.sup.2             1,3-Phenylenediamine-                         1-[4'-Chloro-6'-(3"-                                      yellowish             4-sulfonic acid                         sulfo-1"-phenyl-                                      red                         amino)-triazinyl-                         amino]-8-hydroxy-                         naphthalene-4,6-                         disulfonic acid    100  Cl           A.sup.1             1,3-Phenylenediamine-                         1-(2'-Methyl-4'-                                      greenish             4-sulfonic acid                         sulfophenyl)-3-                                      yellow                         carboxypyrazol-                         5-one    101  F A.sup.1             1,3-Phenylenediamine-                         1-(4'-sulfophenyl)-                                      greenish             4-sulfonic acid                         3-carboxypyrazol-                                      yellow                         5-one    102  Cl           A.sup.1             1,3-Phenylenediamine-                         5-Aminocarbonyl-1-                                      greenish             4,6-disulfonic acid                         ethyl-2-hydroxy-4-                                      yellow                         methylpyrid-6-one    103  Cl           A.sup.1             1,4-Phenylenediamine-                         4,6-Dihydroxy-2-                                      reddish             2,5-disulfonic acid                         isopropoxypyrimidine                                      yellow    104  Cl           A.sup.1             1,3-Phenylenediamine-                         1-[3'-<3"-(5"'-                                      greenish             4-sulfonic acid                         chloro-4"'-fluoro-                                      yellow                         pyridazin-6"'on-                         1"'-yl)-propionyl>-                         aminophenyl]-3-car-                         boxypyrazol-5-one    105  Cl           A.sup.1             1,3-Phenylenediamine-                         1-[3'-<3"-(5"'-                                      greenish             4,6-disulfonic acid                         chloro-4"'-fluoro-                                      yellow                         pyridazin-6"'on-                         1"'-yl)-propionyl>-                         aminophenyl]-3-car-                         boxypyrazol-5-one    106  Cl           A.sup.1             1,4-Phenylenediamine-                         1-[3'-<3"-(5"'-                                      reddish             2,5-disulfonic acid                         chloro-4"'-fluoro-                                      yellow                         pyridazin-6"'on-                         1"'-yl)-propionyl>-                         aminophenyl]-3-car-                         boxypyrazol-5-one    107  Cl           A.sup.1             1,3-Phenylenediamine-                         1-Hydroxynaphtha-                                      yellowish             4,6-disulfonic acid                         lene-4,8-disulfonic                                      red                         acid    108  Cl           A.sup.1             1,3-Phenylenediamine-                         1-Hydroxynaphthal-                                      yellowish             4,6-disulfonic acid                         ene-4-sulfonic acid                                      red    109  Cl           A.sup.1             1,3-Phenylenediamine-                         2-(3'-Sulfophenyl-                                      brown             4,6-disulfonic acid                         amino)-8-hydroxy-                         naphthalene-6-sul-                         fonic acid    110  Cl           A.sup.1             1,4-Phenylenediamine-                         2-(3'-Sulfophenyl-                                      brown             2,5-disulfonic acid                         amino)-8-hydroxy-                         naphthalene-6-sul-                         fonic acid    111  F A.sup.1             1,4-Phenylenediamine-                         2-(4'-Carboxyphenyl-                                      brown             2,5-disulfonic acid                         amino)-8-hydroxy-                         naphthalene-6-sul-                         fonic acid    112  Cl           A.sup.2             1,3-Phenylenediamine-                         1-(2'-Methyl-4'-                                      yellow             4-sulfonic acid                         sulfophenyl)-3-                         carboxypyrazol-5-one    113  Cl           A.sup.2             1,3-Phenylenediamine-                         5-Aminocarbonyl-1-                                      greenish             4,6-disulfonic acid                         ethyl-2-hydroxy-4-                                      yellow                         methylpyrid-6-one    114  F A.sup.2             1,3-Phenylenediamine-                         4-Amino-6-hydroxy-2-                                      yellow             4,6-disulfonic acid                         morpholinopyrimidine    115  Cl           A.sup.2             1,3-Phenylenediamine-                         2-(3'-Sulfophenyl-                                      brown             4,6-disulfonic acid                         amino)-8-hydroxynaph-                         thalene-6-sulfonic                         acid    116  F A.sup.2             1,3-Phenylenediamine-                         2-Phenylamino-8-                                      brown             4,6-disulfonic acid                         hydroxynaphthalene-                         6-sulfonic acid    117  Cl           A.sup.2             1,4-Phenylenediamine-                         1-Hydroxynaphthal-                                      red             2,5-disulfonic acid                         ene-4-sulfonic acid    118  Cl           A.sup.2             1,3-Phenylenediamine-                         1-Hydroxynaphthal-                                      red             2-sulfonic acid                         ene-3,6-disulfonic                         acid    119  Cl           A.sup.2             1,3-Phenylenediamine-                         1-Hydroxynaphthal-                                      red             2-sulfonic acid                         ene-3,8-disulfonic                         acid    120  Cl           A.sup.2             1,3-Phenylenediamine-                         1-Hydroxynaphthal-                                      red             2-sulfonic acid                         ene-4,8-disulfonic                         acid    __________________________________________________________________________

EXAMPLE 121

54.5 parts of the dye obtained by coupling diazotized2-aminonaphthalene-3,6,8-trisulfonic acid to 3-aminophenylurea aredissolved in 500 parts of water to give a neutral solution, and are thenreacted with 19 parts of cyanuric chloride at pH 6. Thereafter, 24 partsof 1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one are added, andthe mixture is stirred for 4 hours at 30°-35° C. The dye is precipitatedwith potassium chloride and dried under mild conditions. It dyes cottonin fast golden yellow hues, and is of the formula ##STR51##

EXAMPLE 122

47 parts of the primary condensate obtained from cyanuric chloride and1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved, at 0° C.and pH 6, in 600 parts of water, and 23.9 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 80 parts ofdimethylformamide are added. The mixture is heated to 35°-40° C., andthe pH is kept at 6 by the addition of 13.8 parts of sodium bicarbonate.After 1-2 hours, the mixture is cooled to 5° C. with ice, and 25.3 partsof the product obtained by diazotizing aniline-2,5-disulfonic acid in asolution containing hydrochloric acid are added. The pH is kept at 5-6during the coupling by adding 18.8 parts of sodium bicarbonate. The dyeis isolated by adding potassium chloride, and is dried. An aqueoussolution of the resulting dark red powder dyes cotton in brilliantbluish red hues.

The dye is of the formula ##STR52##

EXAMPLE 123

25.3 parts of the product obtained by diazotizing aniline-2,5-disulfonicacid in a solution containing hydrochloric acid are added to a solutionof 47 parts of the primary condensate, obtained from cyanuric chlorideand 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, in 600 parts ofwater. Coupling is carried out at 5° C. and pH 5-6, by adding 18.5 partsof sodium bicarbonate. 23.9 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 100 parts ofdimethylformamide are added to the reaction mixture, the temperature isincreased to 35°-40° C., and the pH is kept slightly acidic during thecondensation by adding 12.8 parts of sodium bicarbonate. The reactionmixture is cooled, and the dye is precipitated with potassium chlorideand dried. Its constitution and properties correspond to those of thedye described in Example 122.

EXAMPLE 124

If the 1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one used inExamples 122 and 123 is replaced with 23.9 parts of1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one, a dye havingsimilar properties is obtained.

Further dyes according to the invention are listed in Table 6, wherecolumns I and II show the diazo component and coupling component used,column III indicates the type of halogen atom present on the triazineradical and capable of being eliminated, column IV gives the radical ofthe amine bonded to the triazine ring, and column V states the hueobtained on cotton.

                                      TABLE 6    __________________________________________________________________________    Example         I         II             III                                    IV                                      V    __________________________________________________________________________    125  Aniline-2-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      red         sulfonic acid                   lene-3,6-disulfonic acid    126  Aniline-4-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      yellowish         sulfonic acid                   lene-4,6-disulfonic acid                                      red    127  4-Methoxy-3-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      dull blu-         sulfoaniline                   lene-3,6-disulfonic acid                                      ish red    128  4-Methyl-2-                   1-Amino-8-hydroxynaphtha-                                  F A.sup.2                                      bluish         sulfoaniline                   lene-3,6-disulfonic acid                                      red    129  2-Naphthylamine-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.1                                      bluish         1,5-disulfonic                   lene-3,6-disulfonic acid                                      red         acid    130  4-Carboxyaniline                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.1                                      bluish                   lene-3,6-disulfonic acid                                      red    131  2-Naphthylamine-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      dull blu-         3,6,8-trisul-                   lene-3,6-disulfonic acid                                      ish red         fonic acid    132  4-(2'-Sulfato-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      bluish         ethylsulfonyl)-                   lene-3,6-disulfonic acid                                      red         aniline    133  1-(4'-Aminophe-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      dull blu-         nyl)-5-chloro-4-                   lene-3,6-disulfonic acid                                      ish red         fluoropyridazin-         6-one    134  4-(2'-Sulfato-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      dull blu-         ethylaminosul-                   lene-4,6-disulfonic acid                                      ish red         fonyl)-aniline    135  3-(4',6'-Dichlo-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      bluish         rotriazinyl-                   lene-3,6-disulfonic acid                                      red         amino)-6-sulfo-         aniline    136  3-[4'-Chloro-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      bluish         6'-(2",5"-disul-                   lene-3,6-disulfonic acid                                      red         fo-1"-phenylami-         no)-triazinyl-         amino]-6-sulfo-         aniline    137  3-<4'-Chloro-6'-                   1-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      bluish         [4"-(2"'-sulfato-                   lene-3,6-disulfonic acid                                      red         ethylsulfonyl)-         phenyl-1"-amino]-         triazinylamino>-         6-sulfoaniline    138  Aniline-2,5-di-                   2-Amino-5-hydroxynaphtha-                                  Cl                                    A.sup.1                                      yellowish         sulfonic acid                   lene-7-sulfonic acid                                      orange    139  2-Methyl-4,6-di-                   2-Amino-5-hydroxynaptha-                                  Cl                                    A.sup.2                                      orange         sulfoaniline                   lene-7-sulfonic acid    140  2-Naphthylamine-                   2-Amino-5-hydroxynaphtha-                                  Cl                                    A.sup.2                                      orange         1,5-disulfonic                   lene-7-sulfonic acid         acid    141  2-Naphthylamine-                   2-Amino-5-hydroxynaphtha-                                  F A.sup.2                                      yellowish         3,6,8-trisulfo-                   lene-7-sulfonic acid                                      red         nic acid    142  3-[4'-Chloro-6'-                   2-Amino-5-hydroxynaphtha-                                  Cl                                    A.sup.2                                      orange         (2",5"-disulfo-                   lene-7-sulfonic acid         1"-phenylamino)-         triazinylamino]-         6-sulfoaniline    143  2-Methyl-4,6-                   2-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.1                                      yellowish         disulfoaniline                   lene-6-sulfonic acid                                      red    144  4-Methoxy-2,5-                   2-Amino-8-hydroxynaphtha-                                  Cl                                    A.sup.2                                      yellowish         disulfoaniline                   lene-6-sulfonic acid                                      red    145  2-Naphthylamine-                   2-Amino-8-hydroxynaphtha-                                  F A.sup.2                                      yellowish         1,5-disulfonic                   lene-6-sulfonic acid                                      red         acid    146  2-Naphthylamine-                   2-Amino-8-hydroxynaphtha-                                  F A.sup.2                                      red         3,6,8-trisulfo-                   lene-6-sulfonic acid         nic acid    147  3-[4'-Chloro-6'-                   2-Amino-8-hydroxynaphtha-                                  F A.sup.2                                      yellowish         (2",5"-disulfo-                   lene-6-sulfonic acid                                      red         1"-phenylamino)-         triazinylamino]-         6-sulfoaniline    148  2-Aminonaphtha-                   3-Aminophenylurea                                  Cl                                    A.sup.2                                      golden         lene-3,6,8-tri-              yellow         sulfonic acid    149  Aniline-2,5-                   3-Aminophenylurea                                  Cl                                    A.sup.2                                      yellow         disulfonic acid    150  2-Aminonaphtha-                   3-Aminophenylurea                                  Cl                                    A.sup.2                                      golden         lene-4,6,8-tri-              yellow         sulfonic acid    151  2-Aminonaphtha-                   3-Propionylaminoaniline                                  Cl                                    A.sup.2                                      golden         lene-4,6,8-tri-              yellow         sulfonic acid    152  2-Aminonaphtha-                   2-Methoxy-5-methylani-                                  Cl                                    A.sup.2                                      golden         lene-4,6,8-tri-                   line               yellow         sulfonic acid    153  2-Aminonaphtha-                   3-Aminophenylurea                                  Cl                                    A.sup.2                                      golden         lene-6,8-disul-              yellow         fonic acid    154  2-Aminonaphtha-                   3-Aminophenylurea                                  F A.sup.2                                      golden         lene-3,6,8-tri-              yellow         sulfonic acid    155  2-Aminonaphtha-                   5-Chloro-2-methoxy-                                  Cl                                    A.sup.2                                      golden         lene-4,6,8-tri-                   aniline            yellow         sulfonic acid    156  2-Aminonaphtha-                   1-Aminonaphthalene-                                  Cl                                    A.sup.2                                      golden         lene-4,8-disul-                   8-sulfonic acid    yellow         fonic acid    157  2-Aminonaphtha-                   3-Aminophenylurea                                  F A.sup.1                                      golden         lene-3,6,8-tri-              yellow         sulfonic acid    158  2-Aminonaphtha-                   3-Propionylaminoani-                                  Cl                                    A.sup.1                                      golden         lene-4,6,8-tri-                   line               yellow         sulfonic acid    159  2-Aminonaphtha-                   2-Methoxy-5-methyl-                                  Cl                                    A.sup.1                                      golden         lene-4,6,8-tri-                   aniline            yellow         sulfonic acid    __________________________________________________________________________

EXAMPLE 160

31.8 parts of a suspension of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 300 parts of waterare added, at 5° C., to 17.3 parts of the product obtained bydiazotizing aniline-4-sulfonic acid in a solution containinghydrochloric acid. Coupling is carried out overnight at pH 1-2, afterwhich 38.6 parts of a suspension of the product obtained by diazotizing,in a solution containing hydrochloric acid, the primary condensate ofcyanuric chloride and 1,3-phenylenediamine-4-sulfonic acid are added.Coupling is completed in a slightly acidic medium by adding 17.8 partsof sodium carbonate; thereafter, a solution of 23.9 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 100 parts ofdimethylformamide is added. Condensation is carried out at 40° C. withthe addition of 16.6 parts of sodium bicarbonate, and the dye isprecipitated with sodium chloride and dried. The resulting black powderdyes cotton in fast navy hues. The dye is of the formula ##STR53##

Further dyes according to the invention are summarized in Table 7, wherecolumn I shows the diazo component used for the acidic coupling, columnII indicates the diazo component used for the coupling in neutral oralkaline solution, column III indicates the type of halogen atom presenton the triazine radical and capable of being eliminated, column IV givesthe radical of the amine bonded to the triazine, and column V states thehue obtained on cotton.

                  TABLE 7    ______________________________________    Ex-    am-    ple  I            II             III IV  V    ______________________________________    161  Aniline-2,5-di-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             navy         sulfonic acid                      4-sulfonic acid    162  2-Chloro-4,6-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             reddish         disulfoaniline                      4-sulfonic acid        navy    163  2-Methyl-4,6-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             reddish         disulfoaniline                      4-sulfonic acid        navy    164  2-Naphthylamine-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             navy         1,5-disulfonic                      4-sulfonic acid         acid    165  2-Naphthylamine-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             navy         3,6,8-trisulfo-                      4-sulfonic acid         nic acid    166  4-(2'-Sulfato-                      1,3-Phenylenediamine-                                     Cl  A.sup.2                                             navy         ethylsulfonyl)-                      4-sulfonic acid         aniline    167  4-(2'-Sulfato-                      1,3-Phenylenediamine-                                     Cl  A.sup.1                                             navy         ethylaminosul-                      4-sulfonic acid         fonyl)-aniline    168  3-[4'-Chloro-                      1,3-Phenylenediamine-                                     F   A.sup.2                                             navy         6'-(4"-sulfo-                      4-sulfonic acid         1"-phenylamino)-         triazinylamino]-         6-sulfoaniline    169  3-(4',6'-Di- 1,3-Phenylenediamine-                                     Cl  A.sup.2                                             navy         chlorotriazinyl-                      4-sulfonic acid         amino)-6-sulfo-         aniline    170  3-[4'-Chloro-                      1,3-Phenylenediamine-                                     Cl  A.sup.1                                             navy         6'-(3"-sulfo-                      4-sulfonic acid         1"-phenylamino)-         triazinylamino]-         6-sulfoaniline    171  3-[4'-Chloro-                      1,3-Phenylenediamine-                                     Cl  A.sup.1                                             navy         6'-(2",5" -disul-                      4-sulfonic acid         fo-1"-phenyl-         amino)-triazinyl-         amino]-6-sulfo-         aniline    ______________________________________

EXAMPLE 172

38.6 parts of the primary condensate obtained from cyanuric chloride and1,3-phenylenediamine-4-sulfonic acid are diazotized in a solutioncontaining hydrochloric acid, and a suspension of 31.8 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 300 parts of wateris added. Coupling is completed at pH 3-4, with the addition of 14.8parts of sodium acetate. 25.4 parts of the product obtained bydiazotizing aniline-2,5-disulfonic acid in a solution containinghydrochloric acid are added, and coupling is completed in a slightlyacidic medium, with the addition of 16.4 parts of sodium carbonate. Asolution of 23.9 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 100 parts ofdimethylformamide is added to the reaction mixture, and the pH is keptat 6-7, at 40° C., with 16.5 parts of sodium bicarbonate. The dye isprecipitated with potassium chloride, and is dried. The resulting blackpowder dyes cotton in fast navy hues. The dye described in Example 172is of the formula ##STR54##

Further dyes according to the invention are summarized in Table 8, wherecolumn I shows the diazo component used for the acidic coupling, columnII indicates the diazo component used for the coupling in neutral oralkaline solution, column III gives the type of halogen atom present onthe triazine radical and capable of being eliminated, column IV givesthe radical of the amine bonded to the triazine, and column V states thehue obtained on cotton.

    ______________________________________    Ex-    am-    ple  I            II             III IV  V    ______________________________________    173  1,3-Phenylenedi-                      2-Naphthylamine-1,5-                                     Cl  A.sup.2                                             navy         amine-4-sulfonic                      disulfonic acid         acid    174  1,3-Phenylenedi-                      Aniline-4-sulfonic acid                                     Cl  A.sup.2                                             navy         amine-4-sulfonic         acid    175  1,3-Phenylenedi-                      2-Naphthylamine-3,6,8-                                     F   A.sup.2                                             navy         amine-4-sulfonic                      trisulfonic acid         acid    176  1,3-Phenylenedi-                      2-Chloro-4,6-disulfo-                                     Cl  A.sup.1                                             navy         amine-4-sulfonic                      aniline         acid    177  1,3-Phenylenedi-                      2-Methyl-4,6-disulfo-                                     Cl  A.sup.2                                             navy         amine-4-sulfonic                      aniline         acid    178  1,3-Phenylenedi-                      4-(2'-Sulfatoethylsul-                                     Cl  A.sup.2                                             navy         amine-4-sulfonic                      fonyl)-aniline         acid    179  1,3-Phenylenedi-                      4-(2'-Sulfatoethyl-                                     Cl  A.sup.2                                             navy         amine-4-sulfonic                      aminosulfonyl)-aniline         acid    180  1,3-Phenylenedi-                      3-(4',6'-Dichlorotri-                                     Cl  A.sup.2                                             navy         amine-4-sulfonic                      azinylamino)-6-sulfo-         acid         aniline    181  1,3-Phenylenedi-                      3-[4'-Chloro-6'-(2",5"-                                     Cl  A.sup.1                                             navy         amine-4-sulfonic                      disulfo-1"-phenyl-         acid         amino)triazinyl-                      amino]-6-sulfoaniline    182  1,3-Phenylenedi-                      3-[4'-Chloro-6'-(4"-                                     F   A.sup.1                                             navy         amine-4-sulfonic                      sulfo-1"-phenylamino)-         acid         triazinylamino]-6-                      sulfoaniline    ______________________________________

EXAMPLE 183

53.7 parts of diazotized1-amino-4-(4",8"-disulfonaphth-2-yl)-azonaphthalene-6-sulfonic acid arecoupled to 22.3 parts of 1-aminonaphthalene-6/7-sulfonic acid at a pHobtained with acetic acid. The mixture is then reacted with 19 parts ofcyanuric chloride at pH 6-7 and 10°-20° C., and, using 24 parts of1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one, a chlorine atom onthe triazine ring is exchanged. The dye is isolated by salting out withpotassium chloride, and is dried under mild conditions. It dyes cottonin reddish brown hues, and is of the formula ##STR55##

Further dyes according to the invention are listed in Table 9, wherecolumn I shows the diazo component used instead of2-aminonaphthalene-4,8-dsulfonic acid, columns II and II indicate thecoupling components used instead of 1-aminonaphthalene-6- and-6/7-sulfonice acid respectively, column IV gives the radical of theamine bonded to the triazine ring, column V indicates the type ofhalogen atom present on the triazine ring and capable of beingexchanged, and column VI states the hue obtained on cotton.

                                      TABLE 9    __________________________________________________________________________    Ex-    ample        I        II       III      IV                                     V VI    __________________________________________________________________________    184 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     Cl                                       reddish        lene-4,8-disul-                 lene-6-sulfonic                          lene-6-sulfonic                                       brown        fonic acid                 acid     acid    185 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     Cl                                       reddish        lene-4,8-disul-                 lene-6/7-sul-                          lene-8-sulfonic                                       brown        fonic acid                 fonic acid                          acid    186 Aniline-2,5-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     Cl                                       reddish        disulfonic acid                 lene-6/7-sul-                          lene-8-sulfonic                                       brown                 fonic acid                          acid    187 Aniline-2,5-                 2,5-Dimethyl-                          1-Aminonaphtha-                                   A.sup.2                                     Cl                                       yellowish        disulfonic acid                 aniline  lene-8-sulfonic                                       brown                          acid    188 1-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.2                                     Cl                                       reddish        lene-2,5,7-tri-                 lene     lene-6-sulfonic                                       brown        sulfonic acid     acid    189 1-Aminonaphtha-                 2,5-Dimethyl-                          1-Aminonaphtha-                                   A.sup.2                                     Cl                                       yellowish        lene-2,5,7-tri-                 aniline  lene-6-sulfonic                                       brown        sulfonic acid     acid    190 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.2                                     Cl                                       reddish        lene-4,8-disul-                 lene-6-sulfonic                          lene-6,8-disul-                                       brown        fonic acid                 acid     fonic acid    191 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     Cl                                       reddish        lene-6,8-disul-                 lene-6/7-sul-                          lene-6-sulfonic                                       brown        fonic acid                 fonic acid                          acid    192 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     Cl                                       reddish        lene-4,6,8-tri-                 lene     lene-6-sulfonic                                       brown        sulfonic acid     acid    193 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.1                                     F reddish        lene-4,8-disul-                 lene-6/7-sul-                          lene-6-sulfonic                                       brown        fonic acid                 fonic acid                          acid    194 2-Aminonaphtha-                 1-Aminonaphtha-                          1-Aminonaphtha-                                   A.sup.2                                     F reddish        lene-6,8-disul-                 lene-6/7-sul-                          lene-6-sulfonic                                       brown        fonic acid                 fonic acid                          acid    __________________________________________________________________________

EXAMPLE 195

6.1 parts of the dye of the formula ##STR56## are dissolved in 80 partsof N-methylpyrrolidone, and 3.6 parts of ClCO--A³ are added at 30°-40°C. Stirring is continued for 1 hour, after which the dye of the formula##STR57## is obtained using 100 parts of saturated potassium chloridesolution.

Yield: 20 parts (dye content: about 30%).

The dyes below, of the general formula ##STR58## were obtained in asimilar manner. The starting materials used are known.

                  TABLE 10    ______________________________________    Ex-    am-    ple  G.sup.1                  G.sup.2                                        Hue    ______________________________________    196          ##STR59##               A.sup.1                                        medium blue    197  "                        A.sup.2                                        reddish                                        blue    198  "                        A.sup.3                                        reddish                                        blue    199  "                        A.sup.5                                        reddish                                        blue    200          ##STR60##               A.sup.3                                        reddish blue    201  "                        A.sup.1                                        neutral                                        blue    202  "                        A.sup.2                                        neutral                                        blue    203          ##STR61##               A.sup.1                                        neutral blue    204  "                        A.sup.2                                        neutral                                        blue    205  "                        A.sup.3                                        neutral                                        blue    206  "                        A.sup.4                                        neutral                                        blue    207          ##STR62##               A.sup.1                                        blue    208  "                        A.sup.2                                        "    209          ##STR63##               A.sup.1                                        "    210  "                        A.sup.2                                        "    211  "                        A.sup.3                                        "    212  "                        A.sup.4                                        "    213          ##STR64##               A.sup.1                                        "    214  "                        A.sup.2                                        "    215  "                        A.sup.3                                        "    216          ##STR65##               A.sup.3                                        "    217          ##STR66##               A.sup.2                                        medium blue    218  "                        A.sup.3                                        medium                                        blue    219          ##STR67##               A.sup.2                                        medium blue    220  "                        A.sup.3                                        medium                                        blue    221          ##STR68##               A.sup.2                                        medium blue    222          ##STR69##               A.sup.1                                        medium blue    223  "                        A.sup.2                                        medium                                        blue    ______________________________________

EXAMPLE 224

69 parts of the dye of the formula ##STR70## are prepared in aconventional manner. 23 parts of the amine H₂ N--A² are added to thereaction solution at 20° C., and the pH is brought to 7 by slowly adding10% strength sodium carbonate solution. Salting out with NaCl gives 74parts of the blue dye of the formula ##STR71##

The dyes below were synthesized in a similar manner: ##STR72##

                  TABLE 11    ______________________________________    Ex-    am-    ple  G.sup.3                    G.sup.4                                          Hue    ______________________________________    225                                    A.sup.1                                          blue    226          ##STR73##                 A.sup.1                                          "    227  "                          A.sup.2                                          "    228          ##STR74##                 A.sup.1                                          "    229  "                          A.sup.2                                          "    230          ##STR75##                 A.sup.2                                          "    ______________________________________

EXAMPLE 231

The procedure described in Example 224 is followed, except that, insteadof the amine H₂ N--A², the amine reacted is one obtained by acylatingmetamic acid with the acid chloride ClCO--A³. In this manner, 80 partsof the dye of the formula ##STR76## are obtained.

Dyes of the general formula ##STR77## were synthesized in a similarmanner.

                                      TABLE 12    __________________________________________________________________________    Example         G.sup.5                    G.sup.6                                      Hue    __________________________________________________________________________    232          ##STR78##                 A.sup.1                                      reddish blue    233          ##STR79##                 A.sup.2                                      reddish blue    234          ##STR80##                 A.sup.1                                      reddish blue    235          ##STR81##                 A.sup.2                                      reddish blue    236          ##STR82##                 A.sup.3                                      reddish blue    237          ##STR83##                 A.sup.3                                      blue    238          ##STR84##                 A.sup.2                                      blue    239          ##STR85##                 A.sup.1                                      blue    240          ##STR86##                 A.sup.2                                      blue    241          ##STR87##                 A.sup.3                                      blue    242          ##STR88##                 A.sup.1                                      blue    243          ##STR89##                 A.sup.2                                      blue    244          ##STR90##                 A.sup.3                                      blue    245          ##STR91##                 A.sup.1                                      blue    246          ##STR92##                 A.sup.2                                      blue    247          ##STR93##                 A.sup.3                                      blue    __________________________________________________________________________

EXAMPLE 248

15.8 parts of the compound of the formula ##STR94## and 1,500 parts ofwater are heated to 45° C., the pH being brought to 9 with sodiumhydroxide solution. The mixture is cooled to 0°-5° C., the pH is reducedto 7 with hydrochloric acid, and a fine suspension of 9.7 parts ofcyanuric chloride in 100 parts of ice water is then added. The mixtureis stirred at 0°-5° C., and the pH is kept at from 6.5 to 7 with sodiumcarbonate until the reaction is complete, this requiring about 11/2hours. A solution of 12.7 parts of1-(3'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 50 parts ofN-methylpyrrolidone is then added dropwise in the course of 10 minutes.The temperature is increased to 40° C., and the mixture is stirred,while maintaining the pH at 6.5, until the reaction is complete. Themixture is then cooled to 20° C., salting out is effected with 400 partsof sodium chloride, and the precipitated dye is filtered off undersuction and dried. It dyes cellulose fibers in reddish blue hues whichhave good fastness properties, and is of the formula ##STR95##

EXAMPLE 249

23 parts of the compound corresponding roughly to the formula ##STR96##are dissolved in 450 parts of water, and a solution of 6.1 parts of1-(2'-chlorocarbonylethyl)-5-chloro-4-fluoropyridazin-6-one in 25 partsof ethyl acetate is added dropwise at 0°-5° C. The temperature is thenallowed to increase to 25° C. in the course of 11/2 hours, whilestirring thoroughly, the pH being kept at 6-6.5 by the addition ofsodium bicarbonate. The mixture is stirred at this temperature until thepH remains constant, after which salting out is effected with sodiumchloride, and the dye is filtered off under suction and dried. It dyescellulose fibers in reddish blue hues, and corresponds roughly to theformula ##STR97##

The dyes listed in the Table below can be prepared in a similar manner;the radical ##STR98## is abbreviated to ##STR99##

                                      TABLE 13    __________________________________________________________________________    Ex-    am-    ple       X                                             Anchor    Hue    __________________________________________________________________________    250                                                      ##STR100##                                                               reddish blue    251       "                                                      ##STR101##                                                               reddish blue    252       "                                             COA.sup.2 reddish                                                               blue    253       "                                             COA.sup.4 reddish                                                               blue    254       "                                             COA.sup.5 reddish                                                               blue    255        ##STR102##                                                      ##STR103##                                                               reddish                                                               violet    256        ##STR104##                                   COA.sup.3 red    257        ##STR105##                                                      ##STR106##                                                               reddish blue    258       "                                                      ##STR107##                                                               reddish blue    259       "                                             COA.sup.1 reddish                                                               blue    260       "                                             COA.sup.2 reddish                                                               blue    261       "                                             COA.sup.3 reddish                                                               blue    262        ##STR108##                                                      ##STR109##                                                               reddish blue    263        ##STR110##                                   COA.sup.3 reddish blue    264        ##STR111##                                                      ##STR112##                                                               reddish blue    265        ##STR113##                                   COA.sup.2 reddish blue    266        ##STR114##                                                      ##STR115##                                                               reddish blue    267        ##STR116##                                                      ##STR117##                                                               reddish blue    268        ##STR118##                                   COA.sup.2 reddish blue    269        ##STR119##                                   COA.sup.1 red    270        ##STR120##                                                      ##STR121##                                                               red    271        ##STR122##                                                      ##STR123##                                                               red    272        ##STR124##                                                      ##STR125##                                                               blue    273        ##STR126##                                                      ##STR127##                                                               reddish blue    274        ##STR128##                                   COA.sup.3 reddish blue    275        ##STR129##                                                      ##STR130##                                                               reddish blue    276        ##STR131##                                                      ##STR132##                                                               reddish blue    276a        ##STR133##                                                      ##STR134##                                                               reddish blue    276b        ##STR135##                                                      ##STR136##                                                               reddish    __________________________________________________________________________                                                               blue

EXAMPLE 277

48.5 parts of copper phthalocyanine tetrasulfonyl chloride are stirredwith a mixture of 125 parts of ice and 125 parts of water, and asolution of 14.4 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 50 parts ofdimethylformamide is added dropwise at 0°-5° C. Thereafter, the pH isbrought to 6 with sodium bicarbonate, and the mixture is heated to 30°C. in the course of 1 hour and to 40° C. in the course of a furtherhour, and is kept at this temperature for 3 hours, the pH being keptconstantly at 6-6.5. Salting out is then effected with sodium chloride,and the dye is filtered off under suction and dried. It correspondsroughly to the formula ##STR137## and dyes cellulose material ingreenish blue hues.

EXAMPLE 278

19.7 parts of the compound of the formula ##STR138## are stirred with125 parts of ice and 125 parts of water to give a homogeneous mixture,and the pH is brought to 7-7.5 with sodium hydroxide solution. Asolution of 5.7 parts of1-(2'-chlorocarbonylethyl)-5-chloro-4-fluoropyridazin-6-one in 45 partsof chloroform is added dropwise at 10° C. in the course of 10 minutes.The mixture is then stirred at 10°-15° C., and the pH is kept at 6.5-7by the addition of sodium carbonate. After about 1 hour, the pH remainsconstant; the dye, the preparation of which is complete, is then meltedout with sodium chloride, filtered off under suction and dried. Itcorresponds roughly to the formula ##STR139## and dyes cellulosematerial in fast greenish blue hues.

EXAMPLE 279

58 parts of the compound corresponding roughly to the formula ##STR140##are stirred with 300 parts of water and 125 parts of ice to give ahomogeneous mixture, and the pH is brought to 7 with sodium hydroxidesolution. A fine suspension of 16.6 parts of cyanuric chloride in 170parts of ice water is then added at 0°-5° C., the pH being kept at5.3-5.5 with 10% strength sodium hydroxide solution. When the reactionis complete, a solution of 21.6 parts of1-(4'-aminophenyl)-5-chloro-4-fluoropyridazin-6-one in 60 parts ofdimethylformamide is added dropwise. The mixture is then heated to35°-40° C. and kept at this temperature for 4 hours, the pH beingmaintained at 6 with sodium bicarbonate. The mixture is then cooled,salting out is effected with sodium chloride, and the dye is filteredoff under suction and dried. It corresponds roughly to the formula##STR141##

The dyes listed in the Table below can be prepared in a similar manner.They are of the general formula ##STR142## where n and m are each 0, 1,2 or 3 and r is 1, 2, 3 or 4.

                                      TABLE 14    __________________________________________________________________________                                                      approximate                                                      values    Example         Me     L.sup.7                  L.sup.8                    L.sup.10                A         n  m r  Hue    __________________________________________________________________________    280  Cu     H H                     ##STR143##                                             ##STR144##                                                      2  1 1  greenish blue    281  Cu     --                  --                    HNCH.sub.2CH.sub.2NH                                             ##STR145##                                                      3  0 1  greenish blue    282  Cu     --                  --                     ##STR146##             COA.sup.2 1,7                                                         0 1,8                                                              greenish blue    283  Cu     --                  --                     ##STR147##                                             ##STR148##                                                      3  0 1  greenish blue    284  Cu     H H                     ##STR149##                                             ##STR150##                                                      2  1 1  greenish blue    284a Ni     H H                     ##STR151##                                             ##STR152##                                                      2  1 1  turquoise                                                              green    285  Cu     --                  --                     ##STR153##             COA.sup.3 1  0 3  greenish blue    286  Cu     H H                     ##STR154##             COA.sup.2 1,6                                                         1 1  greenish blue    287  Cu     --                  --                    direct bond             NHA.sup.2 3  0 1  greenish                                                              blue    288  Cu     H H                     ##STR155##             COA.sup.3 2  1 1  greenish blue    289  Ni     --                  --                     ##STR156##                                             ##STR157##                                                      3  0 1  bluish green    289a Ni     --                  --                     ##STR158##                                             ##STR159##                                                      1.7                                                         0 1.8                                                              bluish green    290  Ni     --                  --                     ##STR160##                                             ##STR161##                                                      3  0 1  green    291  Ni     --                  --                     ##STR162##                                             ##STR163##                                                      2  0 1,5                                                              green    292          ##STR164##                --                  --                    NHCH.sub.2CH.sub.2NH                                             ##STR165##                                                      3-4                                                         0 2-3                                                              green    293  Ni     --                  --                     ##STR166##             COA.sup.2 3  0 1  green    __________________________________________________________________________

EXAMPLE 294

64.8 parts of the known dye of the formula ##STR167## are stirred with700 parts of water, and 1 part of wetting agent and 24 parts of thecompound ClCO-A³, dissolved in 100 parts of chloroform, are added. ThepH is increased to 7 in the course of 2 hours by sprinkling in solidsodium bicarbonate.

The dye is obtained from the solution by spray-drying, the yield being73 parts of the dye of the formula ##STR168##

The dyes of the general formula chromophore-G⁷ -G⁸ were synthesized in asimilar manner and by conventional methods, and are summarized in Table15.

The chromophores either are known or were prepared similarly to knowncompounds, using standard methods.

                                      TABLE 15    __________________________________________________________________________    Ex-    am-    ple       Chromophore                        G.sup.7            G.sup.8                                                               Color    __________________________________________________________________________    295        ##STR169##                                           ##STR170##        A.sup.1                                                               blue    296       "                                  "                  A.sup.2                                                               blue    297       "                                           ##STR171##        A.sup.1                                                               blue    298       "                                  "                  A.sup.2                                                               blue    299       "                                           ##STR172##        A.sup.5                                                               blue    300       "                                           ##STR173##        A.sup.3                                                               blue    301        ##STR174##                                           ##STR175##        A.sup.3                                                               blue    302       "                                  "                  A.sup.2                                                               blue    303       "                                           ##STR176##        A.sup.1                                                               blue    304       "                                  "                  A.sup.2                                                               blue    305        ##STR177##                                           ##STR178##        A.sup.3                                                               blue    306       "                                  "                  A.sup.2                                                               blue    307       "                                           ##STR179##        A.sup.2                                                               blue    308       "                                  "                  A.sup.1                                                               blue    309        ##STR180##                                           ##STR181##        A.sup.3                                                               navy    310        ##STR182##                        "                  A.sup.3                                                               blue    311       "                                  "                  A.sup.2                                                               blue    312       "                                           ##STR183##        A.sup.1                                                               blue    313       "                                  "                  A.sup.2                                                               blue    314       "                                           ##STR184##        A.sup.3                                                               blue    315       "                                  "                  A.sup.2                                                               blue    316        ##STR185##                                           ##STR186##        A.sup.3                                                               navy    317        ##STR187##                        "                  A.sup.3                                                               navy    318       "                                  "                  A.sup.1                                                               navy    319       "                                  "                  A.sup.2                                                               navy    320        ##STR188##                        "                  A.sup.3                                                               blue    321        ##STR189##                        "                  A.sup.3                                                               navy    322       "                                           ##STR190##        A.sup.2                                                               navy    323        ##STR191##                                           ##STR192##        A.sup.3                                                               voilet    324       "                                  "                  A.sup.2                                                               violet    325       "                                           ##STR193##        A.sup.2                                                               violet    326        ##STR194##                                           ##STR195##        A.sup.3                                                               navy    327       "                                  "                  A.sup.2                                                               navy    328       "                                           ##STR196##        A.sup.1                                                               navy    329       "                                  "                  A.sup.2                                                               navy    330        ##STR197##                                           ##STR198##        A.sup.3                                                               navy    331        ##STR199##                        "                  A.sup.3                                                               brown    332       "                                  "                  A.sup.2                                                               brown    333       "                                  "                  A.sup.1                                                               brown    334       "                                           ##STR200##        A.sup.2                                                               brown    335        ##STR201##                                           ##STR202##        A.sup.3                                                               brown    336        ##STR203##                        "                  A.sup.3                                                               brown    337        ##STR204##                        "                  A.sup.3                                                               brown    338       "                                  "                  A.sup.2                                                               brown    339       "                                           ##STR205##        A.sup.1                                                               brown    340        ##STR206##                                           ##STR207##        A.sup.3                                                               red    341        ##STR208##                        "                  A.sup.3                                                               bluish red    342       "                                  "                  A.sup.2                                                               bluish                                                               red    343       "                                           ##STR209##        A.sup.2                                                               bluish red    344        ##STR210##                                           ##STR211##        A.sup.3                                                               red    345       "                                  "                  A.sup.2                                                               red    346       "                                           ##STR212##        A.sup.2                                                               red    347        ##STR213##                                           ##STR214##        A.sup.3                                                               violet    348       "                                           ##STR215##        A.sup.2                                                               violet    349        ##STR216##                                           ##STR217##        A.sup.3                                                               violet    350        ##STR218##                        "                  A.sup.3                                                               black    351       "                                  "                  A.sup.1                                                               black    352       "                                  "                  A.sup.2                                                               black    353       "                                           ##STR219##        A.sup.                                                               black    354       "                                  "                  A.sup.1                                                               black    355        ##STR220##                                           ##STR221##        A.sup.3                                                               gray    356        ##STR222##                        "                  A.sup.3                                                               black- ish                                                               gray    357        ##STR223##                        "                  A.sup.3                                                               brown    358       "                                  "                  A.sup.1                                                               brown    359       "                                  "                  A.sup.2                                                               brown    360       "                                           ##STR224##        A.sup.1                                                               brown    361       "                                  "                  A.sup.2                                                               brown    362        ##STR225##                                           ##STR226##        A.sup.3                                                               blue    363       "                                  "                  A.sup.2                                                               blue    364       "                                           ##STR227##        A.sup.2                                                               blue    365       "                                  "                  A.sup.1                                                               blue    366       "                                           ##STR228##        A.sup.1                                                               blue    367        ##STR229##                                           ##STR230##        A.sup.3                                                               blue    368       "                                  "                  A.sup.2                                                               blue    369        ##STR231##                                           ##STR232##        A.sup.3                                                               blue    370        ##STR233##                                           ##STR234##        A.sup.3                                                               blue    371       "                                  "                  A.sup.1                                                               blue    372       "                                  "                  A.sup.2                                                               blue    373       "                                           ##STR235##        A.sup.2                                                               blue    __________________________________________________________________________

EXAMPLE 374

18.8 parts of 1,3-Phenylenediamine-4-sulfonic acid are dissolved in 200parts of water to give a neutral solution, and a solution of 32 parts of3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride in 80parts of chloroform is added dropwise at 10° C., the pH being kept at 7by the addition of 80 parts of 1 molar sodium carbonate solution. After4 hours, the reaction mixture is diazotized in a solution containinghydrochloric acid, and a solution of 39 parts of1-isobutyrylamino-8-hydroxynaphthalene-4,6-disulfonic acid in 300 partsof water is added at 5° C. Coupling is completed in a slightly acidicmedium by adding 15.8 parts of sodium carbonate, and the dye isprecipitated from neutral solution with potassium chloride. The pressedmaterial is freeze-dried. The resulting red powder dyes cotton inbrilliant yellowish red fast hues. The dye is of the formula ##STR236##

Further dyes according to the invention are listed in Table 16, wherecolumn I shows the radical of the carboxylic acid chloride used, columnsII and III indicate the compounds used instead of1,3-Phenylenediamine-4-sulfonic acid and1-isobutyrylamino-8-hydroxynaphthalene-4,6-disulfonic acid, and columnIV states the hue obtained on cotton.

                                      TABLE 16    __________________________________________________________________________    Ex-    ple  I II          III            IV    __________________________________________________________________________    375  A.sup.3           1,3-Phenylenediamine-                       1-Benzoylamino-8-hydroxy-                                      yellowish           4-sulfonic acid                       naphthalene-4,6-disulfo-                                      red                       nic acid    376  A.sup.3           1,3-Phenylenediamine-                       1-Benzoylamino-8-hydroxy-                                      red           4-sulfonic acid                       naphthalene-3,6-disulfo-                       nic acid    377  A.sup.4           1,3-Phenylenediamine-                       1-(3'-Carboxypropionyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-4,6-disulfonic acid    378  A.sup.3           1,4-Phenylenediamine-                       1-Butyrylamino-8-hydroxy-                                      bluish           2-sulfonic acid                       naphthalene-4,6-disulfo-                       nic acid    379  A.sup.3           1,3-Phenylenediamine-                       1-(2'-Carboxy-6'-chloro-                                      red           4-sulfonic acid                       benzoylamino)-8-hydroxy-                       naphthalene-3,6-disulfo-                       nic acid    380  A.sup.2           1,3-Phenylenediamine-                       1-(3'-Sulfopropionyl-                                      red           4-sulfonic acid                       amino)-8-hydroxynaphtha-                       lene-3,6-disulfonic acid    381  A.sup.3           1,3-Phenylenediamine-                       1-(3'-Sulfopropionyl-                                      red           4-sulfonic acid                       amino)-8-hydroxynaphtha-                       lene-3,6-disulfonic acid    382  A.sup.1           1,3-Phenylenediamine-                       1-(Sulfoacetylamino)-8-                                      red           4-sulfonic acid                       hydroxynaphthalene-3,6-                       disulfonic acid    383  A.sup.4           1,3-Phenylenediamine-                       1-(Sulfoacetylamino)-8-                                      yellowish           4-sulfonic acid                       hydroxynaphthalene-4,6-                                      red                       disulfonic acid    384  A.sup.1           1,3-Phenylenediamine-                       1-(3'-Sulfopropionyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-4,6-disulfonic acid    385  A.sup.3           1,3-Phenylenediamine-                       1-(3'-Sulfopropionyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-4,6-disulfonic acid    386  A.sup.3           1,3-Phenylenediamine-                       1-Succinylamino-8-                                      red           4-sulfonic acid                       hydroxynaphthalene-3,6-                       disulfonic acid    387  A.sup.2           1,3-Phenylenediamine-                       1-(2'-Sulfobenzoyl-                                      red           4-sulfonic acid                       amino)-8-hydroxynaphtha-                       lene-3,6-disulfonic acid    388  A.sup.3           1,3-Phenylenediamine-                       1-(2'-Sulfobenzoyl-                                      red           4-sulfonic acid                       amino)-8-hydroxynaphtha-                       lene-3,6-disulfonic acid    389  A.sup.4           1,3-Phenylenediamine-                       1-(2'-Sulfobenzoylamino-                                      yellowish           4-sulfonic acid                       8-hydroxynaphthalene-                                      red                       4,6-disulfonic acid    390  A.sup.2           1,3-Phenylenediamine-                       1-(2'-Sulfobenzoylamino-                                      yellowish           4-sulfonic acid                       8-hydroxynaphthalene-                                      red                       4,6-disulfonic acid    391  A.sup.3           1,3-Phenylenediamine-                       1-(Cyclohexylaminocar-                                      yellowish           4-sulfonic acid                       bonylamino)-8-hydroxy-                                      red                       naphthalene-3,6-disulfonic                       acid    392  A.sup.3           1,3-Phenylenediamine-                       2-(3'-Sulfopropionyl-                                      orange           4-sulfonic acid                       amino)-5-hydroxynaphtha-                       lene-7-sulfonic acid    393  A.sup.1           1,3-Phenylenediamine-                       2-(3'-Sulfopropionyl-                                      orange           4-sulfonic acid                       amino)-5-hydroxynaphtha-                       lene-7-sulfonic acid    394  A.sup.4           1,3-Phenylenediamine-                       2-(Sulfoacetylamino)-5-                                      orange           4-sulfonic acid                       hydroxynaphthalene-7-                       sulfonic acid    395  A.sup.3           1,3-Phenylenediamine-                       2-(Sulfoacetylamino)-5-                                      orange           4-sulfonic acid                       hydroxynaphthalene-7-                       sulfonic acid    396  A.sup.1           1,3-Phenylenediamine-                       2-(2'-Sulfobenzoylamino)-                                      orange           4-sulfonic acid                       5-hydroxynaphthalene-7-                       sulfonic acid    397  A.sup.3           1,3-Phenylenediamine-                       2-(2'-Sulfobenzoylamino)-                                      orange           4-sulfonic acid                       5-hydroxynaphthalene-7-                       sulfonic acid    398  A.sup.3           1,3-Phenylenediamine-                       2-(3'-Sulfopropionyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-6-sulfonic acid    399  A.sup.1           1,3-Phenylenediamine-                       2-(3'-Sulfopropionyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-6-sulfonic acid    400  A.sup.2           1,3-Phenylenediamine-                       2-(Sulfoacetylamino)-8-                                      yellowish           4-sulfonic acid                       hydroxynaphthalene-6-                                      red                       sulfonic acid    401  A.sup.3           1,3-Phenylenediamine-                       2-(Sulfoacetylamino)-8-                                      yellowish           4-sulfonic acid                       hydroxynaphthalene-6-                                      red                       sulfonic acid    402  A.sup.1           1,3-Phenylenediamine-                       2-(2'-Sulfobenzoylamino)-                                      yellowish           4-sulfonic acid                       8-hydroxynaphthalene-6-                                      red                       sulfonic acid    403  A.sup.3           1,3-Phenylenediamine-                       2-(2'-Sulfobenzoylamino)-                                      yellowish           4-sulfonic acid                       8-hydroxynaphthalene-6-                                      red                       sulfonic acid    404  A.sup.3           1,3-Phenylenediamine-                       2-(Sulfomethylamino)-8-                                      red           4-sulfonic acid                       hydroxynaphthalene-6-                       sulfonic acid    405  A.sup.2           1,3-Phenylenediamine-                       2-(Sulfomethylamino)-8-                                      red           4-sulfonic acid                       hydroxynaphthalene-6-                       sulfonic acid    406  A.sup.3           1,4-Phenylenediamine-                       2-(Sulfomethylamino)-8-                                      bluish red           2-sulfonic acid                       hydroxynaphthalene-6-                       sulfonic acid    407  A.sup.3           1,3-Phenylenediamine-                       2-(N--Acetyl-N--methyl-                                      yellowish           4-sulfonic acid                       amino)-8-hydroxynaphtha-                                      red                       lene-6-sulfonic acid    408  A.sup.3           1,3-Phenylenediamine-                       2-(N-- Acetyl-N--methyl-                                      orange                       amino)-5-hydroxynaphtha-                       lene-7-sulfonic acid    409  A.sup.3           1,3-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      greenish           4-sulfonic acid                       boxypyrazolone yellow    410  A.sup.3           1,4-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      reddish           2-sulfonic acid                       boxypyrazolone yellow    411  A.sup.3           1,4-Phenylenediamine-                       1-[5'-(2"-Amino-4"-                                      reddish           2-sulfonic acid                       chlorotriazinylamino)-                                      yellow                       2'-sulfophenyl]-3-car-                       boxypyrazol-5-one    412  A.sup.2           1,3-Phenylenediamine-                       1-(2'-Methyl-4'-sulfo-                                      yellow           4-sulfonic acid                       phenyl)-3-carboxypyrazol-                       5-one    413  A.sup.1           1,3-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      yellow           4-sulfonic acid                       boxypyrazol-5-one    414  A.sup.1           1,3-Phenylenediamine-                       1-(2',4'-Disulfophenyl)-                                      yellow           4-sulfonic acid                       3-methylpyrazol-5-one    415  A.sup.3           1,3-Phenylenediamine-                       5-Aminocarbonyl-1-ethyl-                                      yellow           4-sulfonic acid                       2-hydroxy-4-methylpyrid-                       6-one    416  A.sup.3           1,3-Phenylenediamine-                       1-Ethyl-2-hydroxy-4-methyl-                                      yellow           4-sulfonic acid                       5-sulfomethylpyrid-6-one    417  A.sup.3           1,3-Phenylenediamine-                       4-Amino-6-hydroxy-2-                                      yellow           4-sulfonic acid                       morpholinopyrimidine    418  A.sup.3           1,3-Phenylenediamine-                       1-Hydroxynaphthalene-                                      red           4-sulfonic acid                       4,8-disulfonic acid    419  A.sup.3           1,3-Phenylenediamine-                       1-Hydroxynaphthalene-                                      red           4-sulfonic acid                       3,8-disulfonic acid    420  A.sup.3           1,3-Phenylenediamine-                       1-Hydroxynaphthalene-                                      orange           4-sulfonic acid                       3,6-disulfonic acid    421  A.sup.3           1,3-Phenylenediamine-                       2-(3'-Sulfophenylamino)-                                      brown           4-sulfonic acid                       8-hydroxynaphthalene-6-                       sulfonic acid    422  A.sup.1           1,3-Phenylenediamine-                       1-Hydroxynaphthalene-                                      red           4-sulfonic acid                       3,6,8-trisulfonic acid    423  A.sup.3           1,4-Phenylenediamine-                       1-Hydroxynaphthalene-                                      red           2-sulfonic acid                       3,6,8-trisulfonic acid    424  A.sup.3           1,3-Phenylenediamine-                       1-[4'-<3"-(5"'-Chloro-                                      yellow           4-sulfonic acid                       4"'-fluoropyridazin-6"'-                       on-1"'-yl)-propionyl-                       amino>-phenyl]-3-car-                       boxypyrazol-5-one    425  A.sup.4           1,3-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      yellow           4-sulfonic acid                       boxypyrazol-5-one    426  A.sup.5           1,3-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      yellow           4-sulfonic acid                       boxypyrazol-5-one    427  A.sup.6           1,3-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      yellow           4-sulfonic acid                       boxypyrazol-5-one    428  A.sup.5           1,4-Phenylenediamine-                       1-(4'-Sulfophenyl)-3-car-                                      yellow           2-sulfonic acid                       boxypyrazol-5-one    __________________________________________________________________________

EXAMPLE 429

A solution of 32 parts of3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride in 60parts of ethyl acetate is added dropwise to a solution of 18.8 parts of1,3-phenylenediamine-4-sulfonic acid in 200 parts of water at 10° C.,and the pH is kept at 7 by the addition of 80 parts of 1 molar sodiumcarbonate solution. After 4 hours, the reaction mixture is diazotized ina solution containing hydrochloric acid, and a suspension of 31.8 partsof 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added at 5° C.The pH during the acidic coupling is kept at 3.5 with sodium acetate.17.3 parts of the product obtained by diazotizing aniline-4-sulfonicacid in a solution containing hydrochloric acid are then added, andcoupling is carried out by adding 17.6 parts of sodium carbonate. Thedye is precipitated from the neutral position mixture by adding sodiumchloride, and is then dried. It dyes cotton in fast reddish navy hues,and is of the formula ##STR237##

Further dyes according to the invention are summarized in Table 17,where column I shows the radical of the carboxylic acid chloride used,columns II and III indicate the diazo components used instead of1,3-phenylenediamine-4-sulfonic acid and aniline-4-sulfonic acid, andcolumn IV states the hue obtained on cotton.

                  TABLE 17    ______________________________________    Ex-    am-    ple  I     II           III           IV    ______________________________________    430  A.sup.3               1,3-Phenylenedi-                            Aniline-2,5-disulfonic                                          navy               amine-4-sulfonic                            acid               acid    431  A.sup.4               1,3-Phenylenedi-                            2-Naphthylamine-1,5-                                          navy               amine-4-sulfonic                            disulfonic acid               acid    432  A.sup.5               1,3-Phenylenedi-                            2-Naphthylamine-3,6,8-                                          navy               amine-4-sulfonic                            trisulfonic acid               acid    433  A.sup.5               1,3-Phenylenedi-                            4-Allylsulfoaniline                                          reddish               amine-4-sulfonic           navy               acid    434  A.sup.5               1,3-Phenylenedi-                            4-(2'-Sulfatoethylsul-                                          reddish               amine-4-sulfonic                            fonyl)-aniline                                          navy               acid    435  A.sup.5               1,3-Phenylenedi-                            4-(2'-Sulfatoethylamino-                                          reddish               amine-4-sulfonic                            sulfonyl)-aniline                                          navy               acid    436  A.sup.5               1,3-Phenylenedi-                            1-(3'-Aminophenyl)-5-                                          navy               amine-4-sulfonic                            chloro-4-fluoropyri-               acid         dazin-6-one    437  A.sup.5               1,3-Phenylenedi-                            2-Sulfo-5-(4',6'-di-                                          reddish               amine-4-sulfonic                            chlorotriazinylamino)-                                          navy               acid         aniline    438  A.sup.2               1,3-Phenylenedi-                            Aniline-2,5-disulfonic                                          reddish               amine-4-sulfonic                            acid          navy               acid    439  A.sup.1               1,4-Phenylenedi-                            2-Sulfo-4-(4',6'-di-                                          dark               amine-2-sulfonic                            chlorotriazinylamino)-                                          green               acid         aniline    440  A.sup.2               1,4-Phenylenedi-                            2-Sulfo-3-acetylamino-                                          greenish               amine-2-sulfonic                            aniline       navy               acid    441  A.sup.3               1,3-Phenylenedi-                            2-Sulfo-5-[4'-chloro-                                          reddish               amine-4-sulfonic                            6'-(4" -sulfophenyl-                                          navy               acid         amino)-triazinyl]-                            aminoaniline    442  A.sup.3               1,3-Phenylenedi-                            2-Sulfo-5-[4'-fluoro-6'-                                          reddish               amine-4-sulfonic                            (4"-sulfophenylamino)-                                          navy               acid         triazinyl]-aminoaniline    ______________________________________

EXAMPLE 443

25.4 parts of aniline-2,5-disulfonic acid are diazotized in a solutioncontaining hydrochloric acid, and a suspension of 31.8 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added. Coupling iscarried out overnight in a solution containing hydrochloric acid, afterwhich 31.9 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)propionyl chloride areadded. Thereafter, the mixture is neutralized by adding 17.5 parts ofsodium carbonate, and coupling is carried out. The dye is precipitatedby adding potassium chloride, and is dried under mild conditions. Itdyes cotton in fast greenish navy hues, and is of the formula ##STR238##

Further dyes according to the invention are summarized in Table 18,where columns I and II indicate the diazo components used instead ofaniline-2,5-disulfonic acid and 1,3-phenylenediamine-4-sulfonic acid,column III shows the radical of the carboxylic acid chloride used, andcolumn IV states the hue obtained on cotton.

                                      TABLE 18    __________________________________________________________________________    Example         I             II          III                                     IV    __________________________________________________________________________    444  Aniline-4-sulfonic acid                       1,3-Phenylenediamine-                                   A.sup.4                                     greenish                       4-sulfonic acid                                     navy    445  2-Naphthylamine-1,5-                       1,3-Phenylenediamine-                                   A.sup.3                                     greenish         disulfonic acid                       4-sulfonic acid                                     navy    446  2-Naphthylamine-3,6,8-                       1,3-Phenylenediamine-                                   A.sup.5                                     greenish         trisulfonic acid                       4-sulfonic acid                                     navy    447  3-(2'-Sulfatoethyl-                       1,3-Phenylenediamine-                                   A.sup.2                                     navy         sulfonyl)-aniline                       4-sulfonic acid    448  4-Allylsulfonylani-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         line          4-sulfonic acid                                     navy    449  4-Aminosulfonylani-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         line          4-sulfonic acid                                     navy    450  2-Chloro-4,6-disulfo-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         aniline       4-sulfonic acid                                     navy    451  1-(3'-Aminophenyl)-5-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         chloro-4-fluoropyri-                       4-sulfonic acid                                     navy         dazin-6-one    452  2-Sulfo-5-(4',6'-di-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         chlorotriazinylamino)-                       4-sulfonic acid                                     navy         aniline    453  2-Sulfo-4'-(4',6'-di-                       1,4-Phenylenediamine-                                   A.sup.4                                     dark green         chlorotriazinylamino)-                       2-sulfonic acid         aniline    454  2-Sulfo-5-[4'-chloro-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         6'-(4"-sulfophenyl-                       4-sulfonic acid                                     navy         amino)-triazinylamino]-         aniline    455  2-Sulfo-5-[4'-fluoro-                       1,3-Phenylenediamine-                                   A.sup.3                                     reddish         6'-(4"-sulfophenylamino)-                       4-sulfonic acid                                     navy         triazinylamino]-aniline    __________________________________________________________________________

EXAMPLE 456

21.9 parts of 1-(4'-aminophenyl)-3-carboxypyrazol-5-one are dissolved in250 parts of water to give a neutral solution, and are then reacted, at10°-15° C. and pH 6, with 29 parts of2-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride,dissolved in 50 parts of ethyl acetate. When diazotizable amino groupsare no longer detectable, 30 parts of diazotized2-aminonaphthalene-1,5-disulfonic acid are coupled to the product at pH5-7. The dye is precipitated with potassium chloride and dried undermild conditions. It dyes cotton in fast yellow hues, and is of theformula ##STR239##

Further dyes according to the invention are listed in Table 19, wherecolumn I and II indicate the compounds used instead of2-aminonaphthalene-1,5-disulfonic acid and1-(4'-aminophenyl)-3-carboxypyrazol-5-one respectively, column III showsthe radical of the carboxylic acid chloride used, and column IV statesthe hue obtained on cotton.

                                      TABLE 19    __________________________________________________________________________    Example         I            II           III                                     IV    __________________________________________________________________________    457  Aniline-2,5-disulfonic                      1-(4'-Aminophenyl)-                                   A.sup.3                                     yellow         acid         3-carboxypyrazol-5-one    458  Aniline-2-sulfonic                      1-(5'-Amino-2'-sulfo-                                   A.sup.3                                     greenish         acid         phenyl)-3-carboxypyra-                                     yellow                      zol-5-one    459  1-Acetylamino-3-amino-                      1-(2'-Aminoethyl)-5-                                   A.sup.3                                     greenish         benzene-4,6-disulfonic                      aminocarbonyl-2-                                     yellow         acid         hydroxy-4-methyl-                      pyrid-6-one    460  1-(4',6'-Dichlorotri-                      1-(2'-Aminoethyl)-5-                                   A.sup.5                                     greenish         azinylamino)-3-amino-                      aminocarbonyl-2-                                     yellow         benzene-4,6-disulfonic                      hydroxy-4-methyl-         acid         pyrid-6-one    461  4-Aminoazobenzene-2,4'-                      1-(2'-Sulfophenyl-5'-                                   A.sup.3                                     reddish         disulfonic acid                      amino)-3-carboxypyra-                                     yellow                      zol-5-one    462  Aniline-2-sulfonic acid                      1-Amino-8-hydroxynaph-                                   A.sup.3                                     red                      thalene-3,6-disulfonic                      acid    463  Aniline-4-sulfonic acid                      1-Amino-8-hydroxynaph-                                   A.sup.1                                     red                      thalene-3,6-disulfonic                      acid    464  2-Naphthylamine-1-sul-                      1-Amino-8-hydroxynaph-                                   A.sup.3                                     dull blu-         fonic acid   thalene-3,6-disulfonic                                     ish red                      acid    465  2-Naphthylamine-1,5-                      1-Amino-8-hydroxynaph-                                   A.sup.2                                     bluish red         disulfonic acid                      thalene-3,6-disulfonic                      acid    466  4-Methyl-2-sulfoaniline                      1-Amino-8-hydroxynaph-                                   A.sup.3                                     bluish red                      thalene-4,6-disulfonic                      acid    467  2-Aminonaphthalene-                      1-Amino-8-hydroxynaph-                                   A.sup.5                                     bluish red         3,6,8-trisulfonic acid                      thalene-4,6-disulfonic                      acid    468  4-Aminobenzoic acid                      1-Amino-8-hydroxynaph-                                   A.sup.3                                     dull blu-                      thalene-3,6-disulfonic                                     ish red                      acid    469  4-Methoxy-5-sulfoaniline                      1-Amino-8-hydroxynaph-                                   A.sup.4                                     dull blu-                      thalene-3,6-disulfonic                                     ish red                      acid    470  Aniline-2,5-disulfonic                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     orange         acid         thalene-7-sulfonic                      acid    471  2-Naphthylamine-1,5-                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     orange         disulfonic acid                      thalene-7-sulfonic                      acid    472  2-Methyl-4,6-disulfo-                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     orange         aniline      thalene-7-sulfonic                      acid    473  2-Naphthylamine-3,6,8-                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     yellowish         trisulfonic acid                      thalene-7-sulfonic                                     red                      acid    474  Aniline-4-sulfonic acid                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     orange                      thalene-7-sulfonic                      acid    475  2-Naphthylamine-1,5-di-                      2-N--Methylamino-5-                                   A.sup.4                                     reddish         sulfonic acid                      hydroxynaphthalene-                                     orange                      7-sulfonic acid    476  2-Naphthylamine-3,6,8-                      2-N--Methylamino-5-                                   A.sup.5                                     reddish         trisulfonic acid                      hydroxynaphthalene-                                     orange                      7-sulfonic acid    477  Aniline-2,5-disulfonic                      2-Amino-5-hydroxynaph-                                   A.sup.1                                     orange         acid         thalene-7-sulfonic                      acid    478  2-Naphthylamine-3,6,8-                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     red         trisulfonic acid                      thalene-7-sulfonic                      acid    479  4-Methoxy-2,5-disulfo-                      2-Amino-5-hydroxynaph-                                   A.sup.3                                     red         aniline      thalene-7-sulfonic                      acid    480  Aniline-2,4-disulfonic                      2-N--Methylamino-8-                                   A.sup.3                                     yellowish         acid         hydroxynaphthalene-6-                                     red                      sulfonic acid    __________________________________________________________________________

EXAMPLE 481

The condensate obtained, in accordance with Example 374, from 18.8 partsof 1,3-phenylenediamine-4-sulfonic acid and 32 parts of3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride isdiazotized in aqueous solution, and the product is coupled to 38 partsof 1-[4'-(2"-sulfatoethylsulfonyl)-phenyl]-3-methylpyrazol-5-one at pH5-6. The dye, which is isolated by spray-drying, dyes cotton in fastyellow hues and is of the formula ##STR240##

EXAMPLE 482

31.9 parts of the primary condensate obtained from1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride arediazotized in a solution containing hydrochloric acid, and then added toa solution of 46.7 parts of the primary condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and cyanuric chloride.Coupling is carried out at a pH obtained with acetic acid, 16.2 parts ofsodium bicarbonate being added. The dye is precipitated from neutralsolution by adding sodium chloride, and is dried under mild conditions.It dyes cotton in fast brilliant red hues, and is of the formula##STR241##

Further dyes according to the invention are summarized in Table 20,where column I shows the carboxylic acid chloride used, column IIindicates the diazo component used instead of1,3-phenylenediamine-4-sulfonic acid, column III indicates the couplingcomponent used instead of 1-amino-8-hydroxynaphthalene-3,6-disulfonicacid, column IV gives the triazine used instead of cyanuric chloride,and column V states the hue obtained on cotton.

                                      TABLE 20    __________________________________________________________________________    Example         I           II                      III         IV            V    __________________________________________________________________________    483  A.sup.3           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(3'-sulfo-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  phenylamino)-triazine                      disulfonic acid    484  A.sup.2           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(2',5'-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  disulfophenylamino)-                      disulfonic acid                                  triazine    485  A.sup.4           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Difluoro-6-(4'-sulfo-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  phenylamino)-triazine                      disulfonic acid    486  A.sup.5           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(4'-sulfo-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  phenylamino)-triazine                      disulfonic acid    487  A.sup.6           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(4'-carboxy-                                                yellowish           4-sulfonic acid                      naphthalene-4,6-                                  phenylamino)-triazine                                                red                      disulfonic acid    488  A.sup.3           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-dichloro-6-aminotri-                                                yellowish           4-sulfonic acid                      naphthalene-4,6-                                  azine         red                      disulfonic acid    489  A.sup.3           1,4-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(4'-sulfo-                                                bluish           2-sulfonic acid                      naphthalene-4,6-                                  phenylamino)-triazine                                                red                      disulfonic acid    490  A.sup.3           1,3-Phenylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(2'-sulfo-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  ethyl-methylamino)-tri-                      disulfonic acid                                  azine    491  A.sup.3           2,6-Toluylenediamine-                      1-Amino-8-hydroxy-                                  2,4-Dichloro-6-(4'-sulfo-                                                red           4-sulfonic acid                      naphthalene-3,6-                                  phenylamino)-triazine                      disulfonic acid    492  A.sup. 3           1,3-Phenylenediamine-                      2-Amino-5-hydroxy-                                  2,4-Dichloro-6-(3'-sulfo-                                                orange           4-sulfonic acid                      naphthalene-7-sul-                                  phenylamino)-triazine                      fonic acid    493  A.sup.3           1,3-Phenylenediamine-                      2-Amino-5-hydroxy-                                  2,4-Dichloro-6-(2',5'-disul-                                                orange           4-sulfonic acid                      naphthalene-7-sulfonic                                  fophenylamino)-triazine                      acid    494  A.sup.4           1,3-Phenylenediamine-                      2-Amino-5-hydroxy-                                  2,4-Difluoro-6-(4'-sulfo-                                                orange           4-sulfonic acid                      naphthalene-7-sulfonic                                  phenylamino)-triazine                      acid    495  A.sup.1           1,3-Phenylenediamine-                      2-Amino-5-hydroxy-                                  2,4-Dichloro-6-(2',4'-disulfo-                                                orange           4-sulfonic acid                      naphthalene-7-sulfonic                                  phenylamino)-triazine                      acid    496  A.sup.3           2,6-Toluylenediamine-                      2-N--Methylamino-5-                                  2,4-Dichloro-6-(4'-sulfo-                                                reddish           4-sulfonic acid                      hydroxynaphthalene-7-                                  phenylamino)-triazine                                                orange                      sulfonic acid    497  A.sup.3           1,3-Phenylenediamine-                      2-Amino-8-hydroxynaph-                                  2,4-Dichloro-6-(4'-sulfo-                                                yellowish           4-sulfonic acid                      thalene-6-sulfonic acid                                  phenylamino)-triazine                                                red    498  A.sup.3           1,3-Phenylenediamine-                      2-Amino-8-hydroxynaph-                                  2,4-Dichloro-6-(2',5'-disulfo-                                                yellowish           4-sulfonic acid                      thalene-6-sulfonic acid                                  phenylamino)-triazine                                                red    499  A.sup.4           1,3-Phenylenediamine-                      2-N--Methylamino-8-                                  2,4-Difluoro-6-(3'-sulfo-                                                yellowish           4-sulfonic acid                      hydroxynaphthalene-6-                                  phenylamino)-triazine                                                red                      sulfonic acid    500  A.sup.1           1,3-Phenylenediamine-                      2-N--Methylamino-8-                                  2,6-Dichloro-6-(2',4'-di-                                                yellowish           4-sulfonic acid                      hydroxynaphthalene-6-                                  sulfophenylamino)-triazine                                                red                      sulfonic acid    501  A.sup.5           1,3-Phenylenediamine-                      2-N--Methylamino-8-                                  2,6-Dichloro-6-(2'-sulfo-                                                yellowish           4-sulfonic acid                      hydroxynaphthalene-6-                                  ethyl-methylamino)-triazine                                                red                      sulfonic acid    __________________________________________________________________________

EXAMPLE 502

52.1 parts of the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoroopyridazin-6'-on-1'-yl)-propionyl chloride areadded to a suspension of 33.6 parts of the product obtained bydiazotizing, in a solution containing hydrochloric acid, the primarycondensate of 1,3-phenylenediamine-4-sulfonic acid and cyanuricchloride. Coupling is completed at the pH obtained with acetic acid,17.2 parts of sodium bicarbonate being added, and the dye is thenprecipitated from neutral solution with potassium chloride. The pressedmaterial is spray-dried. The resulting dark red powder dyes cotton infast brilliant red hues. The dye is of the formula ##STR242##

Further dyes according to the invention are summarized in Table 21,where column I gives the triazine used instead of cyanuric chloride,column II indicates the coupling component used instead of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, column III gives thecarboxylic acid chloride used, and column IV states the hue obtained oncotton.

                                      TABLE 21    __________________________________________________________________________    Example         I          II              III                                      IV    __________________________________________________________________________    503  2,4-Dichloro-6-(4'-                    1-Amino-8-hydroxynaphtha-                                    A.sup.3                                      red         sulfophenylamino)-                    lene-3,6-disulfonic acid         triazine    504  2,4-Dichloro-6-(2',-                    1-Amino-8-hydroxynaphtha-                                    A.sup.1                                      red         5'-disulfophenyl-                    lene-3,6-disulfonic acid         amino)-triazine    505  2,4-Dichloro-6-                    1-Amino-8-hydroxynaphtha-                                    A.sup.4                                      red         aminotriazine                    lene-3,6-disulfonic acid    506  2,4-Difluoro-6-(3'-                    1-Amino-8-hydroxynaphtha-                                    A.sup.3                                      red         sulfophenylamino)-                    lene-3,6-disulfonic acid         triazine    507  2,4-Dichloro-6-(4'-                    1-Amino-8-hydroxynaphtha-                                    A.sup.3                                      red         carboxyphenylamino)-                    lene-3,6-disulfonic acid         triazine    508  2,4-Dichloro-6-(3'-                    1-Amino-8-hydroxynaphtha-                                    A.sup.6                                      red         sulfophenylamino)-                    lene-3,6-disulfonic acid         triazine    509  2,4-Dichloro-6-                    1-Amino-8-hydroxynaphtha-                                    A.sup.3                                      red         methoxytriazine                    lene-3,6-disulfonic acid    510  2,4-Dichloro-6-(4'-                    1-Amino-8-hydroxynaphtha-                                    A.sup.3                                      yellowish         sulfophenylamino)-                    lene-4,6-disulfonic acid                                      red         triazine    511  2,4-Dichloro-6-(2',-                    1-Amino-8-hydroxynaphtha-                                    A.sup.5                                      yellowish         5'-disulfophenyl-                    lene-4,6-disulfonic acid                                      red         amino)-triazine    512  2,4-Dichloro-6-(4'-                    2-Amino-5-hydroxynaphtha-                                    A.sup.3                                      orange         sulfophenylamino)-                    lene-7-sulfonic acid         triazine    513  2,4-Dichloro-6-(4'-                    2-N--Methylamino-5-                                    A.sup.3                                      orange         sulfophenylamino)-                    hydroxynaphthalene-7-         triazine   sulfonic acid    514  2,4-Difluoro-6-(4'-                    2-N--Methylamino-5-                                    A.sup.4                                      orange         sulfophenylamino)-                    hydroxynaphthalene-7-         triazine   sulfonic acid    515  2,4-Dichloro-6-                    2-Amino-5-hydroxynaphtha-                                    A.sup.2                                      orange         (2',5'-disulfophenyl-                    lene-7-sulfonic acid         amino)-triazine    516  2,4-Dichloro-6-(3'-                    2-Amino-8-hydroxynaphtha-                                    A.sup.3                                      yellowish         sulfophenylamino)-                    lene-6-sulfonic acid                                      red         triazine    517  2,4-Dichloro-6-(3'-                    2-N--Methylamino-8-hydroxy-                                    A.sup.3                                      yellowish         sulfophenylamino)-                    naphthalene-6-sulfonic                                      red         triazine   acid    518  2,4-Difluoro-6-(4'-                    2-N--Methylamino-8-                                    A.sup.4                                      yellowish         sulfophenylamino)-                    hydroxynaphthalene-6-                                      red         triazine   sulfonic acid    519  2,4-Dichloro-6-                    2-Amino-8-hydroxy-                                    A.sup.1                                      yellowish         (2',5'-disulfo-                    naphthalene-6-sulfonic                                      red         phenylamino)-tri-                    acid         azine    __________________________________________________________________________

EXAMPLE 520

A suspension of 31.6 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 400 parts of wateris added to 64 parts of the product obtained by diazotizing, in asolution containing hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride.Coupling is carried out overnight, the solution being buffered withacetate. The pH is then brought to 6.5-7 for 3 hours, 18.8 parts ofsodium carbonate being added, and coupling is completed. The dye isprecipitated from neutral solution by adding sodium chloride, and isdried. It dyes cotton in fast reddish navy hues, and is of the formula##STR243##

EXAMPLE 521

A suspension of 31.6 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 400 parts of wateris added to 31.9 parts of the product obtained by diazotizing, in asolution containing hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and3-(5'-fluoropyridazin-6'-on-1'-yl)propionyl chloride. Coupling iscarried out overnight, the solution being buffered with acetate, afterwhich 33.7 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and5-chloro-2,4,6-trifluoropyrimidine are added. Coupling is carried out inneutral solution by adding 17.9 parts of sodium carbonate, and the dyeis precipitated with sodium chloride. It dyes cotton in fast reddishnavy hues, and is of the formula ##STR244##

EXAMPLE 522

A suspension of 31.5 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 400 parts of wateris added to 33.7 parts of the product obtained by diazotizing, in asolution containing hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and5-chloro-2,4,6-trifluoropyrimidine. Coupling is carried out overnight,the solution being buffered with acetate, after which 32 parts of theproduct obtained by diazotizing, in a solution containing hydrochloricacid, the primary condensate of 1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)propionyl chloride areadded. Coupling is carried out in neutral solution by adding 18 parts ofsodium carbonate, and the dye is precipitated with sodium chloride. Itdyes cotton in fast reddish navy hues, and is of the formula ##STR245##

EXAMPLE 523

31.9 parts of the primary condensate obtained from1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride arediazotized in a solution containing hydrochloric acid, and the productis added to a suspension of 52.1 parts of the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride.Coupling is completed with the addition of 18.2 parts of sodiumbicarbonate, and the dye is precipitated from neutral solution by addingpotassium chloride. The pressed material is freeze-dried. The dye dyescotton in fast brilliant red hues, and is of the formula ##STR246##

Further dyes according to the invention are summarized in Table 22,where column I gives the carboxylic acid chloride used for the acylationof the diazo component, column II indicates the diazo component usedinstead of 1,3-phenylenediamine-4-sulfonic acid, column III indicatesthe coupling component used instead of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, column IV shows thecarboxylic acid chloride used for the acylation of the couplingcomponent, and column V states the hue obtained on cotton.

                                      TABLE 22    __________________________________________________________________________    Example         I II          III          IV                                      V    __________________________________________________________________________    524  A.sup.3           1,3-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.5                                      red           4-sulfonic acid                       thalene-3,6-disulfonic                       acid    525  A.sup.5           1,3-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.3                                      red           4-sulfonic acid                       thalene-3,6-disulfonic                       acid    526  A.sup.1           1,3-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.3                                      red           4-sulfonic acid                       thalene-3,6-disulfonic                       acid    527  A.sup.3           1,3-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.3                                      yellowish           4-sulfonic acid                       thalene-4,6-disulfonic                                      red                       acid    528  A.sup.3           1,3-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.4                                      yellowish           4-sulfonic acid                       thalene-4,6-disulfonic                                      red                       acid    529  A.sup.3           1,4-Phenylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.3                                      bluish red           2-sulfonic acid                       thalene-4,6-disulfonic                       acid    530  A.sup.3           2,6-Toluylenediamine-                       1-Amino-8-hydroxynaph-                                    A.sup.3                                      yellowish           4-sulfonic acid                       thalene-4,6-disulfonic                                      red                       acid    531  A.sup.3           1,3-Phenylenediamine-                       2-Amino-5-hydroxynaph-                                    A.sup.3                                      orange           4-sulfonic acid                       thalene-7-sulfonic                       acid    532  A.sup.5           1,3-Phenylenediamine-                       2-Amino-5-hydroxynaph-                                    A.sup.3                                      orange           4-sulfonic acid                       thalene-7-sulfonic                       acid    533  A.sup.3           2,6-Toluylenediamine-                       2-Amino-5-hydroxynaph-                                    A.sup.3                                      orange           4-sulfonic acid                       thalene-7-sulfonic                       acid    534  A.sup.3           1,3-Phenylenediamine-                       2-Amino-8-hydroxynaph-                                    A.sup.5                                      yellowish           4-sulfonic acid                       thalene-6-sulfonic                                      red                       acid    535  A.sup.3           1,3-Phenylenediamine-                       2-Amino-8-hydroxynaph-                                    A.sup.3                                      yellowish           4-sulfonic acid                       thalene-6-sulfonic                                      red                       acid    536  A.sup.3           1,3-Phenylenediamine-                       2-Amino-8-hydroxynaph-                                    A.sup.6                                      yellowish           4-sulfonic acid                       thalene-6-sulfonic                                      red                       acid    537  A.sup.3           2,6-Toluylenediamine-                       2-N--Methylamino-8-                                    A.sup.3                                      yellowish           4-sulfonic acid                       hydroxynaphthalene-                                      red                       6-sulfonic acid    __________________________________________________________________________

EXAMPLE 538

33.7 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and5-chloro-2,4,6-trifluoropyrimidine are added to a suspension of 52.1parts of the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride in 500parts of water. Coupling is carried out at the pH obtained with aceticacid. The dye is precipitated from neutral solution by adding sodiumchloride, and is dried. It dyes cotton in fast brilliant red hues, andis of the formula ##STR247##

Further dyes according to the invention are summarized in Table 23,where column I shows the diazo component containing reactive groups,column II indicates the coupling component used instead of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, column III gives thecarboxylic acid chloride used for the acylation of the couplingcomponent, and column IV states the hue obtained on cotton.

                                      TABLE 23    __________________________________________________________________________    Example         I          II             III                                      IV    __________________________________________________________________________    539  2-Sulfo-5-(5'-chloro-                    1-Amino-8-hydroxynaphtha-                                   A.sup.3                                      yellowish         2',6'-difluoropyri-                    lene-4,6-disulfonic acid                                      red         midin-4'-ylamino)-         aniline    540  3-(Sulfatoethylsul-                    1-Amino-8-hydroxynaphtha-                                   A.sup.3                                      red         fonyl)-aniline                    lene-3,6-disulfonic acid    541  4-Allylsulfonylani-                    1-Amino-8-hydroxynaphtha-                                   A.sup.4                                      red         line       lene-3,6-disulfonic acid    542  4-(Sulfatoethylsul-                    1-Amino-8-hydroxynaphtha-                                   A.sup.1                                      red         fonyl)-aniline                    lene-3,6-disulfonic acid    543  4-(Sulfatoethylsul-                    1-Amino-8-hydroxynaphtha-                                   A.sup.5                                      red         fonyl)-aniline                    lene-3,6-disulfonic acid    544  4-(Sulfatoethylsul-                    2-Amino-8-hydroxynaphtha-                                   A.sup.3                                      yellowish         fonyl)-aniline                    lene-6-sulfonic acid                                      red    545  2-Sulfo-5-(5'-chloro-                    2-Amino-8-hydroxynaphtha-                                   A.sup.3                                      yellowish         2',6'-difluoropyri-                    lene-6-sulfonic acid                                      red         midin-4'-ylamino)-         aniline    546  2-Sulfo-5-(5'-chloro-                    2-Amino-5-hydroxynaphtha-                                   A.sup.3                                      orange         2',6'-difluoropyri-                    lene-7-sulfonic acid         midin-4'-ylamino)-         aniline    547  3-(Sulfatoethylsul-                    2-Amino-5-hydroxynaphtha-                                   A.sup.3                                      orange         fonyl)-aniline                    lene-7-sulfonic acid    548  4-(Sulfatoethyl-                    2-N--Methylamino-5-                                   A.sup.3                                      orange         aminosulfonyl)-                    hydroxynaphthalene-7-         aniline    sulfonic acid    __________________________________________________________________________

EXAMPLE 549

19 parts of cyanuric chloride in 100 parts of acetone are added to 31.9parts of the primary condensate obtained from1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride. Themixture is stirred at 5°-10° C. and pH 6, with the addition of 14.3parts of sodium bicarbonate, until diazotizable amino groups are nolonger detectable. A neutral solution of 31.6 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added to thereaction mixture, and stirring is carried out at 35° C. and pH 6-7, withthe addition of 14.8 parts of sodium bicarbonate, until the condensationis complete. 17 parts of the product obtained by diazotizinganiline-2-sulfonic acid in a solution containing hydrochloric acid areadded to the ice-cold reaction mixture, and coupling is carried out in aslightly acidic medium. The dye is precipitated from neutral solution byadding potassium chloride, and is dried. It dyes cotton in fastbrilliant red hues, and is of the formula ##STR248##

EXAMPLE 550

28.1 parts of diazotized 4-(2'-sulfatoethylsulfonyl)-aniline arecoupled, at pH 5-7, to the condensate obtained, in accordance withExample 456, from 21.9 parts of1-(4'-aminophenyl)-3-carboxypyrazol-5-one and 29 parts of3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride. The dyeis precipitated with potassium chloride and is dried under mildconditions. It dyes cotton in fast yellow hues, and is of the formula##STR249##

EXAMPLE 551

33.7 parts of the product obtained by diazotizing the condensate of5-chloro-2,4,6-trifluoropyrimidine and 1,3-phenylenediamine-4-sulfonicacid are coupled, at pH 6, to the condensate obtained, in accordancewith Example 456, from 21.9 parts of1-(4'-aminophenyl)-3-carboxypyrazol-5-one and 29 parts of3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride. The dyeis isolated, and dried under mild conditions. It dyes cotton in fastyellow hues, and is of the formula ##STR250##

EXAMPLE 552

69 parts of2-[4'-(3",6",8"-trisulfonaphth-2"-ylazo)-3'-ureidophenylamino]-4,6-dichlorotriazineare dissolved in 800 parts of water, and are reacted with 40 parts of4-[3'-(5"-chloro-4"-fluoropyridazin-6"-on-1"-yl)propionylamino]-2-aminobenzenesulfonicacid at 30°-40° C. at pH 6.5. The dye is precipitated with potassiumchloride, and is dried under mild conditions. It has good fastnessproperties, dyes cotton in brilliant golden yellow hues, and is of theformula ##STR251##

The same dye is also obtained if 54.5 parts of4-(3',6',8'-trisulfonaphth-2'-ylazo)-3-ureidoaniline are reacted with 56parts of4-[3'-(5"-chloro-4"-fluoropyridazin-6"-on-1"-yl)-propionylamino]-2-(4',6'-dichloro-1',3',5'-triazin-2'-ylamino)-benzenesulfonicacid at 30°-35° C. and pH 6-7.

EXAMPLE 553

32 parts of the product obtained by diazotizing1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added to a solution of 52parts of the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride.Coupling is completed at the pH obtained with acetic acid, 18 parts ofsodium bicarbonate being added. The dye is then precipitated fromneutral solution with potassium chloride, and the pressed material isspray-dried. The resulting red powder dyes cotton in fast brilliant redhues. The dye is of the formula ##STR252##

EXAMPLE 554

If 1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one is usedinstead of 1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one,a similar dye is obtained, which dyes cotton in bluish red hues.

EXAMPLE 555

64.5 parts of the red monoazo dye obtained by coupling 31.9 parts of1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one to 31.9parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in acidicsolution are initially taken as an aqueous solution having a pH of 6.5.40 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride areadded, and coupling is completed in a slightly acidic medium, with theaddition of 1 molar sodium carbonate solution. The dye is precipitatedwith sodium chloride, and the pressed material is freeze-dried. Theresulting black powder dyes cotton in fast reddish navy hues. The dye isof the formula ##STR253##

EXAMPLE 556

If 1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one is usedinstead of 1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one,a dye having similar properties is obtained. It dyes cotton in greenishnavy hues.

EXAMPLE 557

32 parts of the product obtained by diazotizing1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one in asolution containing hydrochloric acid are added to the red monoazo dyeobtained when 39 parts of the primary condensate of1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)propionyl chloride arecoupled, in acidic solution, to 31.9 parts of1-amino-8-hydroxynaphthalene-3,6-disulfonic acid. Coupling is completedat neutral pH, with continuous addition of 1 molar sodium carbonatesolution. The dye is then isolated by adding potassium chloride, and thepressed material is freeze-dried. The resulting black powder dyes cottonin fast greenish navy hues. The dye is of the formula ##STR254##

EXAMPLE 558

If 1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one is usedinstead of 1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one,a dye having similar properties is obtained. It dyes cotton in reddishnavy hues.

EXAMPLE 559

27.9 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid, the primary condensate of1,3-phenylenediamine-4-sulfonic acid and β-chloropropionyl chloride arecoupled, in a solution containing acetic acid, to 52 parts of thecondensate obtained from 1-amino-8-hydroxynaphthalene-3,6-disulfonicacid and 3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)propionyl chloride.The dye is then precipitated from neutral solution with sodium chloride,and the pressed material is spray-dried. The resulting red powder dyescotton in fast brilliant red hues. The dye is of the formula ##STR255##

EXAMPLE 560

51.4 parts of the monoazo dye obtained by coupling 28.7 parts ofdiazotized 4-chloroaniline-2,5-disulfonic acid to 22 parts of1-aminonaphthalene-7-sulfonic acid are diazotized at 10°-15° C. in asolution containing hydrochloric acid. 52 parts of the condensateobtained from 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride areintroduced into the reaction mixture, and coupling is completed in aslightly acidic medium, with continuous addition of 1 molar sodiumcarbonate solution. The dye is precipitated from neutral solution withpotassium chloride, and the pressed material is dried under mildconditions. The resulting dark blue powder dyes cotton in fast navyhues. The dye is of the formula ##STR256##

EXAMPLE 561

If the 4-chloroaniline-2,5-disulfonic acid used in Example 560 isreplaced with 32 parts of1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one, a dyehaving similar properties is obtained.

EXAMPLE 562

62 parts of the monoazo dye obtained when 39.1 parts of the condensateof 1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride arediazotized and then coupled to 22 parts of 1-aminonaphthalene-7-sulfonicacid are diazotized at 10°-15° C. in a solution containing hydrochloricacid. 52 parts of the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-propionyl chloride areadded to the reaction mixture, and coupling is carried out in a slightlyacidic medium, with constant addition of 1 molar sodium carbonatesolution. The dye is precipitated from neutral solution with sodiumchloride, and the pressed material is freeze-dried. The resulting bluishblack powder dyes cotton in fact reddish navy hues.

EXAMPLE 563

If 46.7 parts of the primary condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and cyanuric chlorideare used instead of the condensate stated in Example 562 and obtainedfrom 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)-proponyl chloride, a dyehaving similar properties is obtaned.

EXAMPLE 564

If the condensate obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and2-phenyl-4,6-dichloro-s-triazine is used instead of the condensatestated in Example 563 and obtained from1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and cyanuric chloride,a dye having similar properties is obtained.

EXAMPLE 565

If, instead of the condensate stated in Example 562 and obtained from1,3-phenylenediamine-4-sulfonic acid and3-(5'-chloro-4'-fluoropyridazin-6'-on-1'-yl)propionyl chloride, 32 partsof 1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one are usedas the diazo component, a dye having similar properties is obtained.

EXAMPLE 566

32 parts of the product obtained by diazotizing, in a solutioncontaining hydrochloric acid,1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one are addedto a neutral solution of 22 parts of1,4-dimethyl-6-hydroxypyrid-2-one-5-sulfonic acid in 200 parts of water.Coupling is completed at pH 5-7, and the dye is salted out withpotassium chloride at pH 6.5, and is freeze-dried. It dyes cotton infast brilliant yellow hues, and is of the formula ##STR257##

EXAMPLE 567

If the 1-(3'-amino-4'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-onestated in Example 566 is replaced with1-(4'-amino-3'-sulfophenyl)-5-chloro-4-fluoropyridazin-6-one, a dyehaving similar properties is obtained.

We claim:
 1. A reactive dye compound of the formula ##STR258## whereinR¹ is chlorine, R² is hydrogen, B is a direct bond, aliphatic or asulfo-substituted phenylene radical, and X is an azo dye radical or ananthraquinone radical.
 2. The reactive dye according to claim 1, whereinX is an azo dye radical.
 3. The reactive dye according to claim 1,wherein B is a direct bond or is an ethylene carbonyl bond.